CN112654678A

CN112654678A - Composition, method for producing the same, and dispersant

Info

Publication number: CN112654678A
Application number: CN201980052794.7A
Authority: CN
Inventors: 中村明彦; 高桥花苗; 中村拓马; 田村纯夫; 兼中翼
Original assignee: Nippon Paper Industries Co Ltd
Current assignee: Nippon Paper Industries Co Ltd
Priority date: 2018-08-09
Filing date: 2019-08-08
Publication date: 2021-04-13
Anticipated expiration: 2039-08-08
Also published as: CA3109103A1; EP3835365A1; WO2020032216A1; EP3835365A4; US20210292632A1; CN112654678B; US11873443B2

Abstract

The present invention addresses the problem of providing a solid material of a lignin-containing composition that exhibits high dispersibility and is excellent in heat resistance, a solid material of a high-performance lignin derivative that can be used in applications such as dispersants, can be used easily in construction sites for concrete and the like, and can also be used in premix applications for mixing with hydraulic compositions, or a composition that can be used as a dispersant that can impart thickening properties to various dispersed materials and can improve the properties of the dispersed materials, regardless of the applications such as hydraulic compositions, dyes, inorganic and organic pigments, coal water slurries, agricultural chemicals, kiln industry, and oilfield excavation mud water; the composition contains a lignin sulfonic acid compound and a water-soluble compound, or a lignin derivative which is a reaction product of the lignin sulfonic acid compound and an aromatic water-soluble compound and satisfies a predetermined condition, and is a granular material or a liquid material.

Description

Composition, method for producing the same, and dispersant

Technical Field

The invention relates to a composition, a preparation method thereof and a dispersing agent.

Background

Lignin is a natural high molecular component present in trees and is produced commercially on a large scale in the paper industry where wood is used as a raw material. For example, kraft lignin can be obtained from kraft pulp waste liquor, and lignosulfonic acid can be obtained from sulfite pulp waste liquor. Kraft lignin and lignosulfonic acid, or processed products thereof, are used as dispersants in a wide variety of industrial fields such as dyes, hydraulic compositions (e.g., cement and gypsum), inorganic and organic pigments, coal water slurries, agricultural chemicals, kiln industry, and muddy water for oil field excavation.

Lignin derivatives that are considered to be applied to various applications such as muddy water for oil field excavation have been proposed (see, for example, patent documents 1 and 2). These lignin derivatives show low viscosity values after being subjected to high temperatures and excellent thermal properties.

Further, for example, patent document 3 discloses the use of a modified lignosulfonate for controlling the amount of a sulfonic group, the amount of a carboxyl group, and the molecular weight as a dye dispersant. Patent document 4 discloses the use of a graft copolymer of lignin sulfonic acid and an acrylic or vinyl monomer having a molecular weight distribution within a predetermined range as a cement dispersant. Further, patent document 5 discloses a graft copolymer of acrylic acid and lignosulfonate as a dispersion stabilizer for oilfield excavation mud water. Further, patent document 6 discloses a lignin derivative composed of a reaction product of a lignosulfonate and a water-soluble monomer having a polyoxyalkylene hydrocarbon chain.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2011-240224;

patent document 2: japanese patent laid-open publication No. 2011-240223;

patent document 3: japanese patent laid-open publication No. 2002-146028;

patent document 4: japanese patent laid-open publication No. H01-145358;

patent document 5: specification of U.S. patent No. 4,322,301;

patent document 6: japanese patent No. 5769930.

Disclosure of Invention

Problems to be solved by the invention

It is generally known that lignosulfonic acid has poor heat resistance. Therefore, when the resin composition is used for excavation, cement dispersion at high temperatures such as summer, and the like, heat resistance at higher temperatures is required, and there is room for improvement.

The high-performance lignin derivatives described in patent documents 3 to 6 are liquid products. In the case of a liquid, the water content needs to be recalculated at the construction site, and therefore, a solid is desirable from the viewpoint of ease of handling. In addition, if the liquid material is used, it is difficult to form the solid material in a single package form, and a predetermined amount of the solid material needs to be weighed at a construction site.

When used as a solid substance of lignin derivative, it is necessary to dissolve the lignin derivative in mortar, cement paste, fresh concrete, or the like to exhibit a desired effect.

In addition, the lignin dispersants described in patent documents 3 to 6 have insufficient performance.

A first object of the present invention is to provide a solid of a lignin-containing composition that exhibits high dispersibility and excellent heat resistance.

A second object of the present invention is to provide a high-performance solid lignin derivative which can be used for dispersant applications and the like, can be used easily in concrete construction sites and the like, and can also be used for premix applications to be mixed with a hydraulic composition.

A third object of the present invention is to realize effective utilization of lignin, which is a recyclable biomass resource, from the viewpoint of reducing environmental load in recent years. More specifically, it is intended to provide a composition which can be used as a dispersant for imparting thickening properties to various dispersed materials and improving the properties of the dispersed materials, regardless of the uses such as hydraulic compositions, dyes, inorganic and organic pigments, coal water slurries, agricultural chemicals, sludge for kiln industry and oil field excavation.

Means for solving the problems

The present inventors have conducted intensive studies on the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by containing a lignin sulfonic acid compound and a water-soluble compound or containing a lignin derivative which is a reaction product of a lignin sulfonic acid compound and an aromatic water-soluble compound and satisfying predetermined conditions, and have completed the present invention.

Namely, the present inventors provide the following [1] to [25 ].

[1] A composition (hereinafter also referred to as composition (1)) containing a lignosulfonic acid-based compound and a water-soluble compound.

[2] The composition according to [1], which has a thermogravimetric reduction rate of 50 to 80% as measured by a thermogravimetric differential thermal analysis apparatus, and is in the form of particles.

[3] The composition according to [2], which has a thermal decomposition point of 350 ℃ or more and less than 400 ℃ as measured by a thermogravimetric differential thermal analyzer.

[4] The composition according to [2] or [3], further comprising a lignin derivative which is a reactant of the lignosulfonic acid-based compound and the water-soluble compound.

[5] The composition according to [4], wherein the lignin derivative has an anionic functional group.

[6] The composition according to [4] or [5], wherein the lignin derivative has a polyoxyalkylene chain having an average molar number of addition of alkylene oxide of 25 or more.

[7] The composition according to any one of [4] to [6], wherein a reaction weight ratio ([ L ]/[ M ]) of the lignosulfonic acid-based compound [ L ] to the water-soluble compound [ M ] in the lignin derivative is 1 to 99/99 to 1.

[8] The composition according to any one of [2] to [7], wherein the water-soluble compound is an aromatic water-soluble compound.

[9] The composition according to [8], wherein the aromatic water-soluble compound contains 1 or more selected from an aromatic water-soluble compound having a polyoxyalkylene chain, an aromatic water-soluble compound having a carboxyl group, and an aromatic water-soluble compound having a sulfo group.

[10] The composition according to [8] or [9], which contains a lignin derivative having a reaction rate of the aromatic water-soluble compound of 50% or more.

[11] A dispersant (hereinafter also referred to as dispersant (1)) containing the composition described in any one of [1] to [10 ].

[12] The dispersant according to [11] above, which is a slurry dispersant for oil field excavation or a dispersant for hydraulic compositions.

[13] A composition (hereinafter also referred to as composition (2)) containing a lignin derivative as a reaction product of a lignosulfonic acid-based compound and an aromatic water-soluble compound, the lignin derivative satisfying the following conditions (a) to (B) and being a granular material, or the lignin derivative satisfying the following conditions (1) to (2) and being a liquid material:

condition (a): the average particle diameter is in the range of 30 to 250 μm,

condition (B): a cumulative area of particle diameters of 100 μm or less in a particle size distribution of 15.0% or more;

condition (1): a B-type viscosity of 30 to 100 mPas in the form of a solution containing 30% of nonvolatile components at 100 ℃,

condition (2): the surface tension of the solution is 25 to 55dyne/cm in the form of a solution containing 10% nonvolatile components at 100 ℃.

[14] The composition according to [13] above, which further satisfies the following condition (C) in the case where the composition is the pellet:

condition (C): the tap apparent specific gravity is in the range of 0.1 to 0.7 g/ml.

[15] The composition according to [13] or [14], wherein the lignin derivative has an anionic functional group.

[16] The composition according to any one of [13] to [15], wherein the lignin derivative has a polyoxyalkylene chain having an average molar number of addition of alkylene oxide of 25 or more.

[17] The composition according to any one of [13] to [16], wherein a reaction weight ratio ([ L ]/[ M ]) of the lignosulfonic acid-based compound [ L ] to the aromatic water-soluble compound [ M ] in the lignin derivative is 1 to 99/99 to 1.

[18] The composition according to any one of [13] to [17], wherein the aromatic water-soluble compound contains 1 or more selected from an aromatic water-soluble compound having a polyoxyalkylene chain, an aromatic water-soluble compound having a carboxyl group, and an aromatic water-soluble compound having a sulfo group.

[19] The composition according to any one of [13] to [18], which contains a lignin derivative having a reaction rate of the aromatic water-soluble compound of 50% or more.

[20] A dispersant (hereinafter also referred to as dispersant (2)) containing the composition according to any one of [13] to [19 ].

[21] The dispersant according to [20] above, which is a dispersant for hydraulic compositions.

[22] A hydraulic composition comprising a hydraulic material and the dispersant according to [20] or [21 ].

[23] The hydraulic composition according to [22], which is a cement composition or a gypsum composition.

[24] A method for producing a composition according to any one of [13] to [19], comprising a step of reacting the lignosulfonic acid-based compound with the aromatic water-soluble compound to obtain the lignin derivative.

[25] A method of making a composition, the method of making having: a step of preparing a liquid composition containing a lignin derivative as a reactant of a lignosulfonic acid-based compound and an aromatic water-soluble compound, and a step of drying the liquid composition to obtain a dried solid; the dry solid satisfies the following conditions (A) and (B), and is a granular material:

condition (a): the average particle diameter is in the range of 30 to 250 μm,

condition (B): the cumulative area of the particles having a particle diameter of 100 μm or less in the particle size distribution is 15.0% or more.

Effects of the invention

According to the present invention, a solid of a lignin-containing composition exhibiting high dispersibility and excellent heat resistance can be provided.

Further, according to the present invention, a high-performance solid lignin derivative can be provided which can be used for dispersant applications and the like, can be used easily in concrete construction sites and the like, and can also be used for premix applications to be mixed with hydraulic compositions.

Further, according to the present invention, it is possible to provide a composition which can be used as a dispersant for imparting thickening properties to various dispersed materials and improving the properties thereof, regardless of the uses such as hydraulic compositions, dyes, inorganic and organic pigments, coal water slurries, agricultural chemicals, kiln industry, and oil field excavation slurry.

Drawings

FIG. 1 is a graph showing the particle size distribution of the lignin derivative (1) produced in production example 1.

FIG. 2 is a graph showing the particle size distribution of the lignin derivative (2) produced in production example 2.

FIG. 3 is a graph showing a particle size distribution of Sunflow RH, which is a commercially available product.

Detailed Description

Hereinafter, the present invention will be described in detail based on preferred embodiments. In the present specification, the expression "AA to BB" means AA or more and BB or less. The thermogravimetric differential thermal analysis apparatus is also referred to as "TG-DTA". The term "liquid substance" refers to a concept including an aqueous solution in which a solute is completely dissolved in a solvent, and a suspension in which at least a part of the solute is dispersed in a solvent.

[1. composition (1) ]

The composition (1) of the present invention contains a lignosulfonic acid-based compound and a water-soluble compound. The composition (1) of the present invention preferably has a thermogravimetric decrease rate of 50 to 80% as measured by TG-DTA and is a granular material, and more preferably has a thermal decomposition point of 350 ℃ or higher and lower than 400 ℃ as measured by TG-DTA.

[1-1. Properties ]

The lower limit of the thermogravimetric reduction rate of the composition (1) of the present invention measured by TG-DTA is preferably 50% or more, more preferably 55% or more, and still more preferably 60% or more. If the content is 50% or more, the ash content is low, and the inhibition of the dispersant by inevitable impurities other than lignin derivatives is suppressed, so that high dispersibility can be ensured. The upper limit thereof is preferably 80% or less, more preferably 75% or less, and still more preferably 70% or less. When the content is 80% or less, heat resistance can be secured. Therefore, the thermogravimetric reduction rate by the TG-DTA measurement is preferably 50 to 80%, more preferably 55 to 75%, and still more preferably 60 to 70%.

The lower limit of the thermal decomposition point of the composition (1) of the present invention as measured by TG-DTA is preferably 350 ℃ or higher, more preferably 360 ℃ or higher, and still more preferably 370 ℃ or higher. When the temperature is 350 ℃ or higher, heat resistance can be ensured. The upper limit is less than 400 ℃, preferably 398 ℃ or less, and more preferably 396 ℃. When the temperature is lower than 400 ℃, resinification of the composition (1) is suppressed, and the composition can function as a dispersant or a binder. Therefore, the thermal decomposition point measured by TG-DTA is preferably 350 ℃ or higher and lower than 400 ℃, more preferably 360 to 398 ℃, and still more preferably 370 to 396 ℃.

The thermal decomposition point and the thermogravimetric reduction rate measured by TG-DTA were measured by a thermogravimetric differential scanning calorimetry (TG-DTA) (trade name "STA 7200", manufactured by SII).

More specifically, the values were measured in the following manner. 10g of the composition was dried and solidified. The method of drying and solidifying includes: 1) a method of drying and solidifying at 105 ℃ for 1 day by using a dryer (trade name "forced air thermostat DKM 600", manufactured by Yamato scientific Co.); 2) a method of drying and solidifying at-20 deg.C for 1 day by using a freeze dryer (trade name "FDU-1200", manufactured by Tokyo physical and chemical instruments Co., Ltd.); 3) a method of drying and solidifying the solid at 180 ℃ by using a spray dryer (trade name: TR120, manufactured by PRECI). Then, about 10mg of the solidified sample was heated from 50 ℃ to 600 ℃ at a heating rate of 10 ℃/min under a nitrogen atmosphere. The temperature at which the weight reduction rate of the sample was extremely high was set as the thermal decomposition point, and the weight reduction rate up to 600 ℃ was set as the thermal weight reduction rate. The measurement was performed 3 times on 1 sample, and the average value was obtained.

The thermal decomposition point and the thermogravimetric decrease rate measured by TG-DTA can be adjusted by appropriately adjusting the kind or amount of the lignosulfonic acid-based compound, the water-soluble compound, and the lignin derivative. Particularly, in the case of containing a lignin derivative, the reaction conditions of the lignin derivative can be adjusted by appropriately designing them. More specifically, the reaction temperature and the reaction time can be adjusted by appropriately changing the kind or amount of the reaction initiator, the concentration of the reaction solution, the ratio of the lignosulfonic acid-based compound to the water-soluble compound, the kind or amount of the side chain functional group of the water-soluble compound, and the like.

[1-2. Lignosulfonic acid-based Compound ]

The lignosulfonic acid-based compound is a compound having a skeleton in which a carbon at the α -position of the side chain of the hydroxyphenylpropane structure of lignin is cleaved and a sulfo group (sulfonic acid group) is introduced. The structure of the above-described skeleton portion is shown in formula (1).

[ chemical formula 1]

The lignosulfonic acid-based compound may be a modified compound of a compound having a skeleton represented by the above formula (1) (hereinafter, also referred to as "modified lignosulfonic acid-based compound"). The modification method is not particularly limited, and examples thereof include: hydrolysis, alkylation, alkoxylation, sulfonation, sulfoesterification, sulfomethylation, aminomethylation, desulfonation and other chemical modification methods; a method for fractionating a lignin sulfonic acid compound by ultrafiltration. Among them, as the chemical modification method, 1 or 2 or more modification methods selected from hydrolysis, alkoxylation, desulfonation, and alkylation are preferable.

The lignosulfonic acid-based compound may take the form of a salt. Examples of the salt include: monovalent metal salts, divalent metal salts, ammonium salts, organic ammonium salts. Among these, calcium salts, magnesium salts, sodium salts, calcium-sodium mixed salts, and the like are preferable.

The method and source of the lignosulfonic acid-based compound are not particularly limited, and may be any of natural products and synthetic products. The lignosulfonic acid-based compound is one of the main components of a waste liquor of sulfurous acid pulp obtained by cooking wood under acidic conditions. Accordingly, a lignosulfonic acid-based compound derived from a sulfite pulp waste liquor can be used.

Since the lignin sulfonic acid compound (modified lignin sulfonic acid compound) is rich in a commercially available product, such a commercially available product can be used in the present invention. As commercially available products, there can be exemplified: vanillex HW (manufactured by Nippon paper Co., Ltd.), SunEkis M (manufactured by Nippon paper Co., Ltd.), Pearlex NP (manufactured by Nippon paper Co., Ltd.), and Sunflow RH (manufactured by Nippon paper Co., Ltd.).

The lignosulfonic acid-based compound typically has at least 1 functional group site that is reactive with the water-soluble compound. Examples of such sites include: carboxyl, hydroxyl (phenolic hydroxyl, alcoholic hydroxyl), sulfydryl, sulfo, aromatic ring, ether bond and alkyl chain.

[1-3. Water-soluble Compound ]

The water-soluble compound means a compound exhibiting water solubility. Examples of the water-soluble compound include: an aromatic water-soluble compound having at least 1 aromatic skeleton or a known (co) polymer as a cement dispersant. Among them, the water-soluble compound is preferably an aromatic water-soluble compound having at least 1 aromatic skeleton. The aromatic water-soluble compound is preferably a compound that can react with a main component of the sulfurous acid pulp waste liquid, that is, the sulfurous acid pulp waste liquid, and is preferably a compound that can bond with a functional group (for example, a phenolic hydroxyl group, an alcoholic hydroxyl group, a carboxyl group, or a mercapto group) contained in the lignosulfonic acid compound by a chemical reaction. The form of the chemical reaction is not particularly limited, and examples thereof include: radical reaction, ionic bond, coordinate bond, condensation reaction, reaction accompanied by hydrolysis, reaction accompanied by dehydration, reaction accompanied by oxidation, reaction accompanied by reduction, and reaction accompanied by neutralization.

The aromatic water-soluble compound preferably has at least 1 polar group. This makes it easy to control the physical properties of the composition (1), and also makes the reaction property good when the composition is reacted with a lignosulfonic acid-based compound. The polar group may be an ionic functional group. Examples of the polar group include: carboxyl, hydroxyl, sulfo, nitroxyl, carbonyl, phosphate, amino, epoxy and other functional groups. The aromatic water-soluble compound may be 1 kind alone or a combination of 2 or more kinds.

Examples of the aromatic water-soluble compound include the following [ a ] to [ D ]. The aromatic water-soluble compound is preferably selected from at least 1 of [ A ] to [ C ], and more preferably only [ A ] or a combination of [ A ] with [ B ] and/or [ C ].

([ A ] aromatic water-soluble compound having polyoxyalkylene chain)

The number of carbon atoms of the oxyalkylene unit constituting the polyoxyalkylene hydrocarbon chain (group) is not particularly limited, but is usually 2 to 18, preferably 2 to 4, and more preferably 2 to 3. Examples of the oxyalkylene unit include: ethylene oxide units, propylene oxide units, butylene oxide units. Among them, an ethylene oxide unit or a propylene oxide unit is preferable.

The average addition mole number of the oxyalkylene unit is preferably 25 or more, more preferably 30 or more, and further preferably 35 or more. Thereby, the dispersibility can be made good. The upper limit is preferably 300 or less, more preferably 200 or less, and still more preferably 150 or less. This can suppress a decrease in dispersion retention. Therefore, the average addition mole number is preferably 25 to 300, more preferably 30 to 200, and further preferably 35 to 150. The average molar number of addition is a standard (reference), and [ A ] may have a structure in which an oxyalkylene unit is not repeatedly added (monooxyalkylene group) regardless of whether the above range is satisfied or not.

The polyoxyalkylene hydrocarbon chain may be composed of 1 or 2 or more kinds of oxyalkylene groups alone. The addition form of each oxyalkylene group of the polyoxyalkylene hydrocarbon chain composed of 2 or more oxyalkylene groups may be any of random, block and mixture thereof. The unit at the terminal of the polyoxyalkylene hydrocarbon chain is usually a hydroxyl group, but is not limited thereto, and may be an alkyl ether or a carboxylic acid ester as long as the linkage with the lignosulfonic acid-based compound is not hindered.

Examples of [ A ] include: alkylene oxide-based adducts of aromatic compounds such as phenol, cresol, nonylphenol, naphthol, methylnaphthol, butylnaphthol, bisphenol A and bisphenol S. More specifically, the following are listed: polyoxyalkylene alkylphenyl ethers, polyoxyalkylene phenyl ethers, polyoxyalkylene alkylnaphthyl ethers, and polyoxyalkylene naphthyl ethers. Among these, since the co-condensation property can be made good, a benzene ring derivative is preferable, at least any one of polyoxyalkylene alkyl phenyl ethers and polyoxyalkylene phenyl ethers is more preferable, and polyoxyalkylene phenyl ethers (among them, oxyalkylene addition products to phenol) (for example, poly (ethylene oxide) monophenyl ether, poly (propylene oxide) monophenyl ether, and preferable ranges of the average addition mole number of ethylene oxide units and propylene oxide units are as described above) are further preferable. [A] The number of the compounds may be 1 or a combination of 2 or more.

([ B ] aromatic water-soluble Compound having carboxyl group)

Examples of [ B ] include: naphthalene or benzene ring derivatives having at least 1 carboxyl group. More specifically, the following are listed: isophthalic acid, hydroxynaphthoic acid, benzoic acid, hydroxybenzoic acid, isomers thereof. Since the reactivity is good, o-hydroxybenzoic acid, m-hydroxybenzoic acid and p-hydroxybenzoic acid are preferred. [B] The number of the compounds may be 1 or a combination of 2 or more.

([ C ] aromatic water-soluble compound having a sulfo group)

Examples of [ C ] include: alkyl naphthalene sulfonic acid, alkyl phenol sulfonic acid, aminobenzene sulfonic acid and alkyl benzene sulfonic acid. More specifically, the following are listed: naphthalenesulfonic acid, methylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, phenolsulfonic acid, cresolsulfonic acid, aminobenzenesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, isomers and condensates thereof. Examples of the condensate include: naphthalene sulfonic acid formaldehyde condensate. Since the reactivity is good, phenol derivatives having a sulfo group and aminobenzenesulfonic acid are preferable, and phenolsulfonic acid and aminobenzenesulfonic acid are more preferable. [C] The number of the compounds may be 1 or a combination of 2 or more.

([ D ] other aromatic water-soluble compounds)

Examples of [ D ] include: [A] examples of the aromatic water-soluble compound other than [ C ] include: phenol, cresol and other (alkyl) phenols. [D] The number of the compounds may be 1 or a combination of 2 or more.

(known as a (co) polymer)

Examples of the known (co) polymer include: a polymer derived from a (poly) alkylene glycol alkenyl ether-based monomer; a water-soluble polyalkylene glycol having a hydrogen atom as a both-terminal group; a copolymer having at least 2 kinds of structural units selected from a polyoxyalkylene structural unit, a polycarboxylic acid structural unit and a polyester structural unit (for example, International patent publication No. 2018/56124).

[1-4 ] E other aromatic Compounds ]

The composition (1) of the present invention may contain [ E ] other aromatic compounds in addition to the above-mentioned lignin sulfonic acid compound and water-soluble compound. Examples of [ E ] include: simple aromatic hydrocarbon compounds such as benzene and naphthalene. [E] The number of the compounds may be 1 or a combination of 2 or more.

When the composition (1) of the present invention does not contain a lignin derivative, the weight ratio of the lignosulfonic acid-based compound ([ L ]), the water-soluble compound ([ M ]), and the other aromatic compound ([ E ]) ([ L ]: M ]: E ]) is preferably 30 to 90:10 to 70:0 to 5, more preferably 40 to 85:15 to 60:0 to 3, and still more preferably 50 to 80:20 to 50:0 to 2.

[1-5. Lignin derivatives ]

The composition (1) of the present invention preferably further contains a lignin derivative as a reactant of the lignosulfonic acid-based compound and the water-soluble compound. The lignin derivative is generally a polymer containing a structural unit derived from a lignosulfonic acid-based compound and a structural unit derived from a water-soluble compound. The lignin derivative may contain a structural unit derived from another aromatic compound.

The chemical structure of the lignin derivative is difficult to be determined uniformly by the general formula and the like. This is because lignin, which is a skeleton of the lignosulfonic acid-based compound constituting the lignin derivative, has a very complicated molecular structure.

The lignin derivative preferably has an anionic functional group and/or a polyoxyalkylene hydrocarbon chain in its molecule. This can further improve the dispersibility of the dispersant.

The anionic functional group means a functional group that is in an anionic form in water, and examples thereof include: hydroxyl, carboxyl, sulfo, phosphate, phenolic hydroxyl. Among these, carboxyl group and sulfo group are preferable.

In the lignin derivative, the anionic functional group may be contained in a structural unit derived from the water-soluble compound, may be contained in a part of a structural unit derived from the lignosulfonic acid-based compound, or may be contained in both.

The anionic functional group in the lignin derivative can be quantitatively and qualitatively observed by an instrumental analysis such as NMR and IR.

The lignin derivative preferably has a polyoxyalkylene hydrocarbon chain in its molecule. The number of carbon atoms of the oxyalkylene unit constituting the polyoxyalkylene chain is not particularly limited, but is usually 2 to 18, preferably 2 to 4, and more preferably 2 to 3. Examples of the oxyalkylene unit include: ethylene oxide units, propylene oxide units, butylene oxide units. Among them, an ethylene oxide unit or a propylene oxide unit is preferable.

The average addition mole number of the oxyalkylene unit is preferably 25 or more, more preferably 30 or more, further preferably 35 or more. Thereby, the dispersibility can be made good. The upper limit is preferably 300 or less, more preferably 200 or less, and still more preferably 150 or less. This can suppress the decrease in the dispersion retention property. Therefore, the average addition mole number is preferably 25 to 300, more preferably 30 to 200, and further preferably 35 to 150.

In the lignin derivative, the polyoxyalkylene hydrocarbon chain may be contained in a part of the structural unit derived from the lignosulfonic acid-based compound, may be contained in the structural unit derived from the water-soluble compound, may be contained in both, and is preferably contained in the latter.

The polyoxyalkylene hydrocarbon chain in the lignin derivative can be quantitatively and qualitatively observed by an analysis with an instrument such as NMR and IR.

(preparation of Lignin derivative)

The lignin derivative may be prepared by a method in which a lignosulfonic acid-based compound, a water-soluble compound, and, if necessary, another aromatic compound are reacted. Examples thereof include: a method of chemically bonding the lignosulfonic acid-based compound and the water-soluble compound (a method of bonding a functional group (for example, a phenolic hydroxyl group or an alcoholic hydroxyl group, a carboxyl group, or a mercapto group) in the lignosulfonic acid-based compound and a functional group in the water-soluble compound, or a method of reacting an aromatic skeleton portion of the lignosulfonic acid-based compound with the water-soluble compound or another aromatic compound).

The lignosulfonic acid-based compound used as a raw material for preparing the lignin derivative may be a powder processed product subjected to a powder drying treatment or the like. Since it is in powder form, it is easy to handle.

From the viewpoint of reactivity, the water-soluble compound is preferably an aromatic water-soluble compound having at least 1 aromatic skeleton, more preferably an aromatic water-soluble compound having at least 1 polar group, further preferably 1 or more selected from the above-mentioned [ A ] to [ C ], and further preferably only [ A ] or a combination of [ A ] with [ B ] and/or [ C ].

Hereinafter, a case where an aromatic water-soluble compound is used as the water-soluble compound will be described as an example.

Examples of the method for chemically bonding the lignosulfonic acid-based compound and the aromatic water-soluble compound include: a method of condensing an aromatic water-soluble compound with a lignosulfonic acid-based compound (for example, formaldehyde condensation), a radical reaction, and an ionic bond. More specifically, the following are listed: a method of adding formaldehyde to a lignin sulfonic acid compound to bond the lignin sulfonic acid compound to an aromatic water-soluble compound; a method in which a radical initiator is allowed to act on a lignosulfonic acid-based compound or the like to initiate a hydrogen radical, and the generated radical is allowed to react with at least 1 aromatic water-soluble compound.

The reaction temperature is not particularly limited as long as it is appropriately set according to the solvent used, and is usually 0 to 200 ℃, preferably 45 to 150 ℃. In addition, in the case where a low boiling point compound is used as the reaction solvent, it is preferable to carry out the reaction under pressure using an autoclave in order to increase the reaction rate.

When the aromatic water-soluble compound is reacted with the lignosulfonic acid-based compound, either of a solution reaction and a bulk reaction may be employed. In the case of solution reaction, a solvent may be used. Examples of the solvent include: water; alcohols such as methanol, ethanol, and isopropanol; aromatic hydrocarbons such as benzene, toluene, xylene, etc.; aliphatic hydrocarbons such as cyclohexane and n-hexane; esters such as ethyl acetate (ethyl acetate); ketones such as acetone and methyl ethyl ketone; cyclic ethers such as tetrahydrofuran and dioxane. Among them, at least any one of water and lower alcohols is preferably used, and water is more preferably used. Thus, the problem of solubility of the raw material monomer and the obtained copolymer can be solved, or the solvent removal step can be omitted.

The solvent may be used alone in 1 kind, or 2 or more kinds (for example, a water-alcohol mixed solvent) may be used in combination.

In the preparation of the lignin derivative, an antifoaming agent may be used. This can suppress foaming during the reaction and can construct a uniform reaction system.

In the preparation of the lignin derivative, it is preferable to stably perform the reaction. Therefore, in the case of carrying out the reaction by solution polymerization, the concentration of dissolved oxygen in the solvent to be used at 25 ℃ can be adjusted to a range of preferably 5ppm or less, more preferably 0.01 to 4ppm, still more preferably 0.01 to 2ppm, and still more preferably 0.01 to 1 ppm. The adjustment of the dissolved oxygen concentration may be carried out in the reaction tank or may be carried out in advance before the reaction.

The progress of the reaction is characterized by a significant increase in viscosity. When the desired viscosity is reached, the reaction may be stopped by cooling or neutralization.

In the preparation of the lignin derivative, water may be added for the purpose of controlling the condensation viscosity and condensation time. Further, the pH during the reaction may be adjusted to an appropriate value. The reaction is usually carried out under acidic conditions. In the case where the reaction system is already acidic due to the aromatic compound having a sulfo group and the unreacted acid contained therein, the reaction may be carried out directly in the acidic region. When the reaction system is not acidic, an acid catalyst such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, or p-toluenesulfonic acid may be added in advance to adjust the pH to 2 or less to perform the reaction. The preferred acid is sulfuric acid, and may be an acid other than the specific examples described above, without limitation.

The weight ratio ([ L ]/[ M ]) of the reaction between the lignosulfonic acid-based compound [ L ] and the aromatic water-soluble compound [ M ] constituting the lignin derivative is not particularly limited, but is preferably 99 to 1/1 to 99 (wt%), more preferably 90 to 2/10 to 98 (wt%), and still more preferably 70 to 5/30 to 95 (wt%). When the proportion of the aromatic water-soluble compound [ M ] is 1.0% by weight or more, the obtained lignin derivative can exhibit an effect of improving the properties originally possessed by the lignin skeleton, that is, the dispersibility. On the other hand, when the proportion of the aromatic water-soluble compound [ M ] is 99% by weight or less, the molecular weight is in an appropriate range, the development of the cohesive property is suppressed, and the dispersing performance can be exhibited.

[ L ]/[ M ] can be defined by (the weight of the solid content of the lignosulfonic acid-based compound before reaction)/(the weight of the solid content of the aromatic water-soluble compound before reaction), and measured by this method in examples described later.

The reaction rate of the aromatic water-soluble compound is preferably 50% or more, more preferably 60% or more, and still more preferably 70% or more. By setting the reaction rate to 50% or more, the dispersibility of the obtained lignin derivative can be favorably exhibited.

The reaction rate of the aromatic water-soluble compound can be measured as follows, and is also measured by this method in examples described later. First, in Gel Permeation Chromatography (GPC) measurement, in the case of using UV (detection wavelength of 280nm), peak areas before and after the reaction were compared. When the peak area before the reaction is denoted by [ b ] and the peak area after the reaction is denoted by [ a ], the following formula is used: the reaction rate was calculated as ([ b ] - [ a ])/[ b ].

The reaction weight ratio of the components other than the lignosulfonic acid-based compound (the aromatic water-soluble compound and the other aromatic compound) used in the preparation of the lignin derivative is not particularly limited, but is preferably the following reaction weight ratio. Preferably, the weight ratio of the reaction is [ A ], [ B ], [ C ], ([ D ] + [ E ]) = 50-100 wt%, 0-50 wt% and 0-10 wt%. Wherein [ A ] + [ B ] + [ C ] + [ D ] + [ E ] =100 wt%.

Here, [ A ] - [ E ] corresponds to the above-mentioned compounds.

The reaction solution after the condensation reaction is preferably thermally post-treated at a temperature of 60 to 120 ℃ under a pH condition of 8.0 to 13.0. The thermal post-treatment is usually carried out continuously for 10 minutes to 3 hours. The aldehyde content (e.g., formaldehyde content) of the reaction solution can thereby be significantly reduced. In addition to or as an alternative to the removal of free formaldehyde by means of the so-called Cannizzaro reaction described above, it is of course also possible to carry out other methods of reducing excess formaldehyde, which are known, for example, in the chemical field of melamine-formaldehyde resins and phenol-formaldehyde resins. Examples of such a method include: a formaldehyde absorbent (a small amount of sodium hydrogen sulfite, hydrogen peroxide) was added.

The reaction solution is adjusted to a pH of 1.0 to 4.0, preferably 1.5 to 2.0, whereby the reaction product is precipitated as a solid to settle to the bottom of the reaction vessel. In this case, the aqueous salt solution from which the supernatant is removed is then separated off. The remaining free reaction products, mostly free of salts, are then redissolved in an amount of water that gives the desired solids concentration, whereby the lignin derivatives can be obtained.

The neutralization may be carried out by using a neutralizing agent which neutralizes the reaction product and the catalyst. Examples of the neutralizing agent include: a basic compound (including salts and hydroxides thereof). More specifically, the following are listed: sodium hydroxide, calcium hydroxide, Ba (OH)₂And the like. Thus, calcium sulfate and barium sulfate, which are low in solubility, are formed together with the free sulfuric acid, and are precipitated in the form of gypsum or the like. Therefore, the precipitate can be removed by filtration separation thereafter, and a salt-free polymer can be obtained. In addition, unwanted sodium sulfate can also be removed by dialysis or ultrafiltration.

In the case where by-products such as sodium sulfate, calcium sulfate, and hydrates thereof are produced in the addition and neutralization of the basic compound, it is preferable to add the basic compound in a heated state after the reaction and to improve the removability of the by-products by maintaining the heated state. The heating is preferably carried out at 40 ℃ or higher. The holding time in the heated state is preferably 30 minutes or more.

The lignin derivative may be any one of a free acid and a neutralized salt thereof, as long as it is a reaction product obtained by the above reaction. The neutralized salt is preferred because the polymer is easy to store and use. Examples of the neutralized salt of the reaction product include: alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as calcium salts; an ammonium salt; salts of organic amines.

After the reaction is completed, the concentration of the obtained lignin derivative can be adjusted as necessary.

(physical Properties of Lignin derivative)

The weight average molecular weight of the lignin derivative is not particularly limited, but is preferably 1,000 to 500,000, more preferably 2,000 to 300,000, and still more preferably 5,000 to 100,000. The weight average molecular weight can be measured by a known method of converting the weight average molecular weight into polyethylene glycol by Gel Permeation Chromatography (GPC).

The measurement conditions of GPC were as follows.

A measuring device: tosoh system

The column used: shodex Column OH-pak SB-806HQ, SB-804HQ, SB-802.5HQ

Eluent: 0.05mM sodium nitrate/acetonitrile 8/2(v/v)

Standard substance: polyethylene glycol (manufactured by Tosoh or GL SCIENCE)

A detector: differential refractometer (Tosoh system)

[1-6. optional Components ]

The composition (1) of the present invention may contain any component in addition to the above components as long as the effects of the present invention are not impaired. As the optional components, there may be mentioned: hydraulic composition dispersants (e.g., cement dispersants and gypsum dispersants), slurry dispersants for oil field excavation, dye dispersants, chelating agents, detergents, flocculants, thickeners, coating agents, paints, adhesives, water-absorbent resins, and the like.

[1-7. method for producing composition (1) ]

The composition (1) of the present invention can be prepared as follows: (1) can be produced by separately mixing (blending) a lignin sulfonic acid compound and a water-soluble compound, and then drying them; (2) the lignin can be produced by preparing a lignin derivative which is a reactant of the lignosulfonic acid-based compound and the water-soluble compound, and drying the lignin derivative. In the case of preparing a lignin derivative, a lignosulfonic acid-based compound and a water-soluble compound may be further blended with the prepared lignin derivative. Preparation of the lignin derivative was as described above. The drying method will be explained below.

Examples of the drying method include: a method of neutralizing with a hydroxide of a divalent metal such as calcium or magnesium to prepare a polyvalent metal salt and then drying the salt; a method of drying the silica-based fine powder or other inorganic powder by being carried thereon; a method of drying and solidifying the mixture on a support of a drying device (e.g., a drum drying device, a tray drying device, or a belt drying device) to form a film; a method for drying and solidifying by using a spray dryer.

[2. dispersant (1) ]

The dispersant (1) of the present invention contains the above-mentioned composition (1), and can be used for various applications. Examples thereof include: dispersants for hydraulic compositions (for example, dispersants for cement and dispersants for gypsum), slurry dispersants for oil field excavation, dispersants for dyes, chelating agents, detergents, flocculants, thickeners, coating agents, paints, adhesives, and water-absorbent resins. The composition (1) of the present invention exhibits high dispersibility and is excellent in heat resistance. Therefore, a slurry dispersant for oil field excavation or a dispersant for hydraulic compositions is preferable.

[2-1. slurry dispersant for oilfield excavation ]

The dispersant (1) of the present invention is useful as a slurry dispersant for oil field excavation. The slurry for oilfield excavation is not particularly limited in composition as long as it is used as a fluid circulating in a well during oilfield excavation and/or recovery. The slurry for oilfield excavation can be generally classified into a water system and an oil system, and the water system slurry is preferable. The aqueous muddy water usually contains clay.

Examples of the clay include: montmorillonite and bentonite. Among them, bentonite is preferable.

The pH of the slurry for oilfield excavation is not particularly limited, but is preferably 9 to 13, more preferably 9.5 to 11.5, and still more preferably about 11. The temperature of the slurry for oilfield excavation is not particularly limited, and may be a high temperature (for example, 80 ℃ or higher, preferably 90 ℃ or higher). The dispersant (1) of the present invention is preferably added in an amount of 0.1% by weight or more, more preferably 0.5% by weight or more, based on the weight of the clay in the muddy water. The upper limit is preferably 30% by weight or less, more preferably 20% by weight or less.

[2-2. dispersant for Hydraulic compositions ]

The dispersant (1) of the present invention can also be used as a dispersant for hydraulic compositions. This mode of use will be described below.

Examples of the dispersed material include: various hydraulic materials. The hydraulic material can be classified into a cement composition such as cement or gypsum and other hydraulic materials, and may be any of them. The dispersant (1) of the present invention can be used as a dispersant for hydraulic compositions, and can constitute hydraulic compositions together with the above hydraulic material and water. The hydraulic composition may further contain fine aggregate (sand, etc.) or coarse aggregate (crushed stone, etc.) as required. Examples of the hydraulic material include: grout, mortar, concrete, stucco.

[2-2-1. Cement composition ]

Among hydraulic compositions, a cement composition (a composition containing the dispersant (1) of the present invention, cement and water as essential components) using cement as a hydraulic material is the most general and one of the preferred embodiments. Hereinafter, a case where the hydraulic composition contains cement (cement dispersant) will be described.

The cement that can be used in the cement composition is not particularly limited, and specific examples thereof include the following cements.

Portland cement (normal, early strength, super early strength, moderate heat, sulfate resistance and respective low alkali types); various blended cements (blast furnace cement, silica cement, fly ash cement); white portland cement; alumina cement; ultra-fast hardening cements (single clinker fast hardening cement, double clinker fast hardening cement, magnesium phosphate cement); cement for grouting; oil well cement; low-heat cement (low-heat blast furnace cement, fly ash mixed low-heat blast furnace cement, belite high-content cement); ultra-high strength cement; a cement-based curing material; ecological cement (cement prepared from more than 1 of municipal refuse incineration ash and sewer sludge incineration ash as raw materials).

Other components than the above-mentioned cement may be added to the cement composition. As such components, the following components can be mentioned.

Micro powder (blast furnace slag, fly ash, cinder ash, clinker ash, shell ash, silicon powder, silicon dioxide powder, limestone powder and the like); gypsum; aggregate (gravel, crushed stone, granulated slag, recycled aggregate, silica aggregate, clay aggregate, zircon aggregate, high-alumina refractory aggregate, silicon carbide refractory aggregate, graphite aggregate, chromium-magnesium aggregate, magnesium aggregate and the like).

Every 1m³The cement composition (2) has no particular limitation on the unit water amount, the amount of cement used and the water/cement ratio (weight ratio), and can be widely used from a poor formulation to a rich formulation.

The unit water amount is preferably 100 to 185kg/m³More preferably 120 to 175kg/m³。

The amount of cement used is preferably 200 to 800kg/m³More preferably 250 to 800kg/m³。

The water/cement ratio (weight ratio) is preferably 0.15 to 0.7, more preferably 0.25 to 0.65.

The dispersant (1) of the present invention can be used in a cement composition having a high water reduction ratio, that is, a water/cement ratio (weight ratio) of low (for example, 0.15 to 0.5). In addition, the concrete composition is suitable for high-strength concrete with a large unit cement amount and a small water/cement ratio or concrete with a small amount of cement (unit cement amount) (for example, about 300 kg/m)³The following) poor-mix concrete is also effective.

In a cement composition (for example, in the case of mortar or concrete using hydraulic cement), the lower limit of the amount of the dispersant (1) of the present invention is preferably 0.01% by weight or more, more preferably 0.02% by weight or more, and still more preferably 0.05% by weight or more, in terms of solid content, relative to the weight of cement. When the amount is 0.01% by weight or more, the dispersibility can be sufficiently exhibited. The upper limit is preferably 10.0 wt% or less, more preferably 7.0 wt% or less, and still more preferably 5.0 wt% or less. When the content is 10.0% by weight or less, the effect of improving dispersibility is not substantially saturated, and the composition is economically advantageous, and adverse effects on various properties of mortar and concrete such as retardation of hardening and strength reduction can be suppressed.

Therefore, the amount of the dispersant (1) of the present invention is preferably 0.01 to 10.0% by weight, more preferably 0.02 to 7.0% by weight, and still more preferably 0.05 to 5.0% by weight, based on the weight of cement. Such a blending amount brings various preferable effects such as reduction in unit water amount, increase in strength, and improvement in durability.

The cement composition can also exert high dispersibility and dispersion retention performance in a high water-reducing ratio region. Further, the composition can exhibit sufficient initial dispersibility and viscosity-lowering property even at low temperatures, and can have excellent workability. Therefore, the above cement composition is effective as a raw material for various concretes by hardening.

Examples of concrete include: ready mixed concrete, concrete for concrete secondary products (precast concrete), concrete for centrifugal molding, concrete for vibration rammer utility, steam cured concrete, and shotcrete. Further, there may be mentioned: mortar or concrete requiring high fluidity, such as medium-fluidity concrete (concrete having a slump value of 22 to 25 cm), high-fluidity concrete (concrete having a slump value of 25cm or more and a slump flow value of 50 to 70 cm), self-filling concrete, and self-leveling material.

[2-2-2. Gypsum composition ]

A gypsum composition using gypsum as a hydraulic material (a composition containing the dispersant (1) of the present invention, gypsum and water as essential components) is also general and is one of preferred embodiments of the present invention. Hereinafter, a case where the hydraulic composition contains gypsum (a dispersant for gypsum) will be described.

If the gypsum is calcium sulfate (CaSO)₄) The mineral as the main component is not particularly limited, and examples thereof include: calcium sulfate hemihydrate (CaSO)₄·1/2H₂O: hemihydrate gypsum), calcium sulfate dihydrate (CaSO)₄·2H₂O: dihydrate gypsum) Anhydrous calcium sulfate (CaSO)₄: anhydrous gypsum). Typical gypsum is hemihydrate gypsum. The gypsum may be any of natural gypsum and chemical gypsum. With respect to the natural gypsum, the origin or the shape is not limited. Examples of the chemical gypsum include: phosphoric acid gypsum, flue gas desulfurization gypsum, titanium gypsum, smelting gypsum and fluorgypsum (フッ acid gypsum).

The amount of the dispersant (1) of the present invention is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and still more preferably 0.10% by weight or more, based on the weight of gypsum, in terms of solid content, in the gypsum composition. When the amount is 0.01% by weight or more, the prescribed dispersibility is exhibited. The upper limit is preferably 5.00 wt% or less, more preferably 3.00 wt% or less, and still more preferably 1.00 wt% or less. When the content is 5.00 wt% or less, the hydration delay of gypsum, that is, the hardening delay of gypsum is not caused, and therefore, the gypsum composition functions as a dispersant having excellent workability.

Therefore, the amount of the dispersant (1) of the present invention is preferably 0.01 to 5.00% by weight, more preferably 0.05 to 3.00% by weight, and still more preferably 0.10 to 1.00% by weight, based on the weight of gypsum. Such a blending amount brings various preferable effects such as reduction in unit water amount, increase in strength, improvement in durability, and the like.

The content of water in the gypsum composition is appropriately determined, and is usually 20% by weight or more, preferably 40% by weight or more, relative to the weight of gypsum. The upper limit is usually 150% by weight or less, preferably 100% by weight or less. The gypsum composition may contain gypsum, water, and commonly used additives other than the dispersant of the present invention.

The gypsum composition can be used for building materials such as gypsum boards and plaster, civil engineering materials such as tunnel reinforcements and ground improvement, ceramic model materials, dental model materials, gypsum cast model materials, etc. by hardening treatment such as heating and drying.

[2-2-3. other additives ]

When the dispersant (1) of the present invention is used as a dispersant for hydraulic compositions, the dispersant may contain other active ingredients of cement dispersants or other active ingredients of additives for concrete as long as the above-mentioned composition (1) is contained. In addition, it may be used in combination with other cement dispersants or other additives for concrete. In the present specification, they are collectively referred to as "other additives".

As the active ingredient of other cement dispersant or the active ingredient of other additive for concrete, for example, the following components can be used. The effective components of other cement dispersants and the effective components of other additives for concrete may be used alone in 1 kind, or 2 or more kinds may be used in combination.

A lignosulfonate; a polyol derivative; a naphthalenesulfonic acid-formaldehyde condensate; a melamine sulfonic acid formaldehyde condensate; polystyrene sulfonate; an aminosulfonic acid-based compound such as an aminoarylsulfonic acid-phenol-formaldehyde condensate (e.g., Japanese patent application laid-open No. 1-113419);

a composition consisting of: (a) a component (a) which is at least any one of a copolymer of a polyalkylene glycol mono (meth) acrylate compound and a (meth) acrylic acid compound and a salt thereof, (b) a component (c) which is at least any one selected from a copolymer of a polyalkylene glycol mono (meth) allyl ether compound and maleic anhydride, a hydrolysate thereof, and a salt thereof, and (c) a component (e.g., jp-a-7-267705);

a composition consisting of: a component a comprising a copolymer of a polyalkylene glycol ester of (meth) acrylic acid and (meth) acrylic acid (salt), a component B comprising a specific polyethylene glycol polypropylene glycol compound, and a component C comprising a specific surfactant (see, for example, japanese patent No. 2508113);

a vinyl copolymer containing structural units each composed of a polyethylene (propylene) glycol ester or a polyethylene (propylene) glycol mono (meth) allyl ether of (meth) acrylic acid, (meth) allylsulfonic acid (salt), and (meth) acrylic acid (salt) (e.g., jp 62-216950 a);

a water-soluble vinyl copolymer obtained by aqueous solution polymerization of a polyethylene (propylene) glycol ester of (meth) acrylic acid, a (poly) allylsulfonic acid (salt), and a (meth) acrylic acid (salt) (see, for example, japanese unexamined patent publication No. 1-226757);

copolymers obtained from a polyethylene (propylene) glycol ester of (meth) acrylic acid, (meth) allylsulfonic acid (salt) or p- (meth) allyloxybenzenesulfonic acid (salt) and (meth) acrylic acid (salt) (see, for example, japanese unexamined patent publication No. 5-36377);

copolymers having monomer units each composed of polyethylene glycol mono (meth) allyl ether and maleic acid (salt) (see, for example, Japanese patent laid-open No. 4-149056);

a graft copolymer consisting of the following structural units: a structural unit derived from a polyethylene glycol ester of (meth) acrylic acid, a structural unit derived from (meth) allylsulfonic acid (salt), a structural unit derived from (meth) acrylic acid (salt), a structural unit derived from alkanediol mono (meth) acrylate or polyalkylene glycol mono (meth) acrylate, and a structural unit containing a polymer block obtained by radical polymerization of an α, β -unsaturated monomer having an amide group in the molecule (see, for example, japanese unexamined patent application publication No. 5-170501);

a water-soluble vinyl copolymer obtained by aqueous radical copolymerization of polyethylene glycol mono (meth) allyl ether, polyethylene glycol mono (meth) acrylate, alkyl (meth) acrylate, (meth) acrylic acid (salt) and (meth) allylsulfonic acid (salt) or p- (meth) allyloxybenzenesulfonic acid (salt) (see, for example, japanese unexamined patent publication No. 6-191918);

copolymers obtained by using polyethylene glycol monoallyl ether, a maleic acid-based monomer, and a monomer copolymerizable with these monomers (see, for example, Japanese patent publication No. 58-38380);

a copolymer obtained by neutralizing a copolymer obtained using a polyalkylene glycol mono (meth) acrylate monomer, a (meth) acrylic acid monomer, and a monomer copolymerizable with these monomers with an alkaline substance (see, for example, japanese patent publication No. 59-18338);

a polymer obtained by using a polyalkylene glycol (meth) acrylate having a sulfo group and, if necessary, a monomer copolymerizable therewith, or a polymer obtained by neutralizing the obtained polymer with an alkaline substance (see, for example, Japanese patent application laid-open No. 62-119147);

an esterification reaction product of a copolymer of an alkoxypolyalkylene glycol monoallyl ether and maleic anhydride and a polyoxyalkylene derivative having an alkenyl group at the terminal thereof (see, for example, Japanese patent laid-open No. 6-271347);

an esterification reaction product of a copolymer of an alkoxypolyalkylene glycol monoallyl ether and maleic anhydride and a polyoxyalkylene derivative having a hydroxyl group at the terminal thereof (see, for example, Japanese patent laid-open No. 6-298555);

and polycarboxylic acids (salts) which are copolymers of an alkenyl ether monomer obtained by adding ethylene oxide or the like to a specific unsaturated alcohol such as 3-methyl-3-buten-1-ol, an unsaturated carboxylic acid monomer, and a monomer copolymerizable with these monomers, or salts thereof (see, for example, Japanese patent laid-open No. 62-68806).

Examples of other cement dispersants and other additives for concrete include: water-soluble polymers, polymer emulsions, air entraining agents, cement wetting agents, swelling agents, waterproofing agents, retarding agents, thickening agents, coagulating agents, drying shrinkage reducing agents, strength enhancers, effect promoters, antifoaming agents, AE agents, separation reducing agents, self-leveling agents, rust inhibitors, coloring agents, mildew inhibitors and other surfactants. These may be used alone in 1 kind, or in 2 or more kinds.

Examples of the water-soluble polymer include the following.

Unsaturated carboxylic acid polymers such as polyacrylic acid or a salt thereof (for example, sodium salt), polymethacrylic acid or a salt thereof (for example, sodium salt), polymaleic acid or a salt thereof (for example, sodium salt), acrylic acid-maleic acid copolymer or a salt thereof (for example, sodium salt);

nonionic cellulose ethers such as methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, and hydroxypropyl cellulose;

a polysaccharide derivative having a polysaccharide skeleton of an alkylated or hydroxyalkylated derivative of a polysaccharide (e.g., methylcellulose, ethylcellulose, hydroxyethylcellulose, or hydroxypropylcellulose), wherein a part or all of the hydrogen atoms of the hydroxyl groups are substituted with a hydrophobic substituent having a hydrocarbon chain having 8 to 40 carbon atoms as a partial structure and an ionic hydrophilic substituent having a sulfo group or a salt thereof as a partial structure;

polysaccharides prepared by microbial fermentation, such as yeast glucan, xanthan gum, and β -1, 3-glucan (which may be linear or branched, for example, curdlan, paramylon, pachyman, scleroglucan, and laminarin);

polyacrylamide; polyvinyl alcohol; starch; starch phosphate ester;

sodium alginate; gelatin; and copolymers of acrylic acid having an amino group in the molecule and quaternary compounds thereof.

Examples of the polymer emulsion include: copolymers of various vinyl monomers such as alkyl (meth) acrylates.

Examples of the hardening retarder other than the hydroxycarboxylic acid compound include the following.

Saccharides such as monosaccharides (e.g., glucose, fructose, galactose, sucrose, xylose, apiose, ribose, and isomerized sugar), disaccharides, trisaccharides, oligosaccharides (e.g., dextrin), polysaccharides (e.g., dextran), and sugar compositions (e.g., molasses) containing at least any of these; sugar alcohols such as sorbitol; magnesium silicofluoride; phosphoric acid and salts thereof or boronic acid esters; aminocarboxylic acids and salts thereof; an alkali soluble protein; humic acid; tannic acid; phenol; polyhydric alcohols such as glycerin; phosphonic acids and derivatives thereof such as phosphonic acid, aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1, 1-diphosphonic acid, ethylenediamine tetra (methylenephosphonic acid), diethylenetriamine penta (methylenephosphonic acid), and alkali metal salts and alkaline earth metal salts thereof.

Examples of the early strength agent and the accelerator include the following.

Soluble calcium salts such as calcium chloride, calcium nitrite, calcium nitrate, calcium bromide, and calcium iodide; chlorides such as iron chloride and magnesium chloride; a sulfate salt; potassium hydroxide; sodium hydroxide; a carbonate salt; a thiosulfate salt; formic acid and formate such as calcium formate; an alkanolamine; alumina cement; calcium silicate aluminate, and the like.

Examples of the antifoaming agent other than the oxyalkylene group include the following.

Mineral oil-based antifoaming agents such as kerosene and liquid paraffin; oil and fat-based antifoaming agents such as animal and vegetable oils, sesame oils, castor oils, and alkylene oxide adducts thereof; fatty acid-based antifoaming agents such as oleic acid, stearic acid, and alkylene oxide adducts thereof; fatty acid ester-based antifoaming agents such as glycerol monoricinoleate, alkenyl succinic acid derivatives, sorbitol monolaurate, sorbitol trioleate and natural waxes; alcohol defoaming agents such as octanol, hexadecanol, acetylene alcohol and ethylene glycol; amide defoaming agents such as acrylate polyamines; phosphate ester-based antifoaming agents such as tributyl phosphate and sodium octyl phosphate; metal soap defoaming agents such as aluminum stearate and calcium oleate; silicone defoaming agents such as dimethyl silicone oil, silicone paste, silicone emulsion, organically modified polysiloxane (polyorganosiloxane such as dimethyl polysiloxane), and fluorosilicone oil.

Examples of the AE agent include the following.

A resin soap; saturated or unsaturated fatty acids; sodium hydroxystearate; lauryl sulfate, ABS (alkylbenzenesulfonic acid), LAS (linear alkylbenzenesulfonic acid), alkanesulfonate, polyoxyethylene alkyl (phenyl) ether sulfate, and salts thereof; polyoxyethylene alkyl (phenyl) ether phosphate or a salt thereof; a proteinaceous material; alkenyl sulfosuccinic acids; alpha-olefin sulfonates, and the like.

Examples of the other surfactants include the following.

An aliphatic monohydric alcohol having 6 to 30 carbon atoms in the molecule, such as stearyl alcohol or stearyl alcohol; alicyclic monohydric alcohols having 6 to 30 carbon atoms in the molecule, such as abietyl alcohol (Abiethyl alcohol); a monovalent thiol having 6 to 30 carbon atoms in the molecule, such as dodecyl thiol; alkylphenols having 6 to 30 carbon atoms in the molecule, such as nonylphenol; amines having 6 to 30 carbon atoms in the molecule, such as laurylamine; polyoxyalkylene derivatives obtained by adding 10 moles or more of an alkylene oxide such as ethylene oxide or propylene oxide to a carboxylic acid having 6 to 30 carbon atoms in the molecule such as lauric acid or stearic acid; alkyl diphenyl ether sulfonates obtained by ether-bonding 2 phenyl groups having a sulfo group, which may have an alkyl group or an alkoxy group as a substituent;

various anionic surfactants other than the above; various cationic surfactants such as alkylamine acetate and alkyltrimethylammonium chloride; various nonionic surfactants; and various amphoteric surfactants, and the like.

Examples of the water repellent include the following.

Fatty acids (salts), fatty acid esters, fats and oils, silicones, paraffins, asphalt, waxes, and the like.

Examples of the rust inhibitor include: nitrite, phosphate, zinc oxide.

Examples of the crack reducing agent include: a polyoxyalkyl ether.

Examples of the swelling material include: ettringite series, coal series.

When the dispersant (1) of the present invention is used in combination with other additives, the mixing ratio of the dispersant (1) of the present invention to other additives (i.e., the weight ratio of the dispersant (1) of the present invention to other additives in terms of solid content) is preferably 1 to 99/99-1, more preferably 5 to 95/95-5, still more preferably 10 to 90/90-10, and still more preferably 20 to 80/80-20.

[2-2-4. hydroxycarboxylic acid-based Compound ]

In addition to the above-mentioned other cement dispersants or other additives for concrete, the dispersant (1) of the present invention may be used in combination with a hydroxycarboxylic acid-based compound. This can exhibit a higher dispersion retention performance even in a high-temperature environment.

As the hydroxycarboxylic acid compound, a hydroxycarboxylic acid having 4 to 10 carbon atoms or a salt thereof is preferable. More specifically, the following are listed: inorganic or organic salts of gluconic acid, glucoheptonic acid, arabinonic acid, malic acid, citric acid, sodium, potassium, calcium, magnesium, ammonium, triethanolamine, etc. These hydroxycarboxylic acid compounds may be used alone or in combination of 2 or more.

Among the above hydroxycarboxylic acid compounds, gluconic acid or a salt thereof is preferable. In particular, in the case of poor-mix concrete, it is preferable to use a lignosulfonate-based dispersant as a sulfonic acid-based dispersant having a sulfo group in the molecule, and gluconic acid or a salt thereof as a hydroxycarboxylic acid-based compound.

When the dispersant (1) of the present invention and a hydroxycarboxylic acid compound are used in combination, the mixing ratio of the dispersant (1) of the present invention and the hydroxycarboxylic acid compound (i.e., the weight ratio of the dispersant (1) of the present invention to the hydroxycarboxylic acid compound in terms of solid content) is preferably 1 to 99/99-1, more preferably 5 to 95/95-5, still more preferably 10 to 90/90-10, and still more preferably 20 to 80/80-20.

When 3 components of the dispersant (1) of the present invention, other additives and a hydroxycarboxylic acid compound are used in combination, the mixing ratio of the dispersant (1) of the present invention, other additives and a hydroxycarboxylic acid compound (i.e., the weight ratio of the dispersant (1) of the present invention/other additives/hydroxycarboxylic acid compound in terms of solid content) is preferably 1 to 98/1 to 98/1 to 98, more preferably 5 to 90/5 to 90/5 to 90, still more preferably 10 to 90/5 to 85/5 to 85, and still more preferably 20 to 80/10 to 70/10 to 70.

[3. composition (2) ]

The composition (2) of the present invention contains a lignin derivative as a reactant of a lignosulfonic acid-based compound and an aromatic water-soluble compound, and the lignin derivative satisfies the following conditions (a) to (B) and is a particulate matter (hereinafter referred to as "one embodiment"), or the lignin derivative satisfies the following conditions (1) to (2) and is a liquid matter (hereinafter referred to as "another embodiment").

Condition (a): the average particle diameter is in the range of 30 to 250 μm.

Condition (1): the B-type viscosity at 100 ℃ in the form of a solution containing 30% of nonvolatile components is 30 to 100 mPas.

[3-1 ] one embodiment of the composition (2 ]

One embodiment of the composition (2) of the present invention satisfies the conditions (a) and (B), and is a particulate matter, preferably further satisfies the condition (C).

Condition (a): the average particle diameter is in the range of 30 to 250 μm.

[ Condition (A) ]

The condition (A) is that the average particle diameter is in the range of 30 to 250 μm. Since the average particle diameter is in the range of 30 to 250 μm, the amount of dust is small and the solubility is excellent.

The average particle size determined under the condition (a) is a value obtained by measuring a 3g powder sample under a dry condition with a laser diffraction particle size distribution measuring apparatus (Mastersizer 3000 (Malvern), and the cumulative distribution is 50% with the particle size (μm) on the horizontal axis and the volume (%) on the vertical axis.

[ Condition (B) ]

The condition (B) is that the cumulative area of the particle diameters of 100 μm or less in the particle size distribution is 15.0% or more. The upper limit of the particle size distribution is preferably 95.0% or less, and more preferably 85.0% or less. When the cumulative area of the particle diameters in the particle size distribution is 100 μm or less is in the above range, the particles can be easily mixed uniformly when added to a hydraulic composition.

The particle size distribution determined under the condition (B) is a cumulative distribution in which the horizontal axis represents the particle size (μm) and the vertical axis represents the volume (%) based on the molecular weight distribution obtained by measuring 3g of each powder sample under dry conditions with a laser diffraction particle size distribution measuring apparatus (Mastersizer 3000 (Malvern)). The cumulative area is a cumulative area in which the particle diameter of the cumulative distribution is 100 μm or less.

[ Condition (C) ]

The condition (C) is that the tap apparent specific gravity is in the range of 0.1 to 0.7 g/ml. When the tap apparent specific gravity is in the range of 0.1 to 0.7g/ml, a composition which can reduce dust and has excellent solubility in a solution can be obtained.

The condition (C) is a value measured as follows. First, 10 to 15g of the composition (2) was collected in a graduated test tube (20 mL capacity). The test tube was placed in a specific volume tester (manufactured by Shishan scientific machine) and vibrated 50 times (40 rpm) at a drop height of 5cm, and the volume of the test tube was measured. The apparent specific gravity at tap was calculated by substituting the measurement results into the following equation.

The formula: tap apparent specific gravity (g/mL) = mass of granular composition (g)/volume of test tube after vibration (mL)

[ control method ]

The conditions (a) to (C) can be adjusted by appropriately designing the reaction conditions of the lignosulfonic acid-based compound and the aromatic water-soluble compound and the conditions for drying the reaction product. More specifically, the type or amount of the reaction initiator, the type or amount of the acid catalyst, the concentration of the reaction solution, the ratio of the lignosulfonic acid-based compound to the aromatic water-soluble compound, the type or amount of the side chain functional group of the aromatic water-soluble compound, the reaction temperature, the reaction time, the drying conditions, and the like can be adjusted by appropriately changing the types or amounts of the reaction initiators, the types or amounts of the acid catalysts, the concentrations of the reaction solutions, the types or amounts of.

In one embodiment, the details of the lignin derivative are the same as those described in the composition (1), and the water-soluble compound is not limited to the aromatic water-soluble compound.

[ optional Components ]

One embodiment of the composition (2) of the present invention may contain any component other than the lignin derivative as long as the effects of the present invention are not impaired. Examples of the optional components include, in addition to raw material components such as unreacted lignin sulfonic acid compounds and unreacted aromatic water-soluble compounds: hydraulic composition dispersants (e.g., cement dispersants and gypsum dispersants), slurry dispersants for oil field excavation, dye dispersants, chelating agents, detergents, flocculants, thickeners, coating agents, paints, adhesives, water-absorbent resins, and the like.

[ method for producing one embodiment of composition (2) ]

The method for producing the composition (2) according to one embodiment is a method for producing a granular composition, which includes a step of preparing a liquid composition containing a lignin derivative as a reactant of a lignosulfonic acid-based compound and an aromatic water-soluble compound, and a step of drying the liquid composition to obtain a dried solid, wherein the dried solid satisfies the conditions (a) and (B).

Condition (a): the average particle diameter is in the range of 30 to 250 μm.

The steps for preparing the liquid composition containing the lignin derivative, and the conditions (a) and (B) are as described above. Therefore, a method for obtaining a dry solid will be described below.

Examples of the method for obtaining a dry solid include: a method of neutralizing with a hydroxide of a divalent metal such as calcium or magnesium to prepare a polyvalent metal salt and then drying the salt; a method of drying the silica-based fine powder or other inorganic powder by being carried thereon; a method of drying and solidifying the mixture on a support of a drying device (e.g., a drum drying device, a tray drying device, or a belt drying device) to form a film; a method for drying and solidifying by using a spray dryer.

[3-2 ] other embodiments of the composition (2) ]

In another embodiment of the composition (2) of the present invention, the lignin derivative satisfies the conditions (1) and (2) and is a liquid substance. Therefore, thickening properties are imparted to the composition, and the composition can be improved, and therefore, the composition can be used for various applications.

When the composition (2) of the present invention is used as a dispersant in another embodiment, it can exhibit very high dispersing performance for various dispersed materials compared with conventional lignin-derived dispersants, regardless of the uses such as hydraulic compositions, dyes, inorganic and organic pigments, coal water slurries, agricultural chemicals, sludge water for kiln industry and oil field excavation. Therefore, other embodiments of the composition (2) of the present invention can be used as a dispersant that can be used in fields where it has been difficult to use lignin-derived dispersants so far.

When a conventional lignin-based dispersant is used for a hydraulic composition, there is a possibility that separation of raw materials (cement, coarse aggregate, fine aggregate, gypsum) of the hydraulic composition from water, that is, so-called feathering (sheeting), occurs. On the other hand, when the dispersant according to another embodiment using the composition (2) of the present invention is used for dispersing a hydraulic composition, the occurrence of feathering is suppressed, the separation of the raw materials of the hydraulic composition from water is suppressed, and the hardening strength of the resulting hydraulic composition can be improved.

The dispersant of the other embodiment using the composition (2) of the present invention is extremely excellent in compatibility with conventional lignin dispersants and polycarboxylic acid dispersants, and can be suitably used in various fields. For example, when used as a dispersant for concrete, the dispersant can exhibit higher dispersibility in a wide range of water-cement ratios by using the dispersant in combination with a conventional dispersant.

Another embodiment of the composition (2) of the present invention is a liquid. If the dispersion medium is in the form of a liquid, it can be easily mixed with a substance to be dispersed, and can be prepared as a dispersion medium which can easily exhibit desired dispersion performance.

[ Lignin derivatives ]

In other embodiments of the composition (2) of the invention, the lignin derivative satisfies "condition (1): a B-type viscosity of 30 to 100 mPas "in the form of a solution containing 30% of nonvolatile components at 100 ℃, and" condition (2): the surface tension of the solution is 25 to 55dyne/cm when the nonvolatile component is 10% at 100 ℃.

Here, the "nonvolatile matter at 100 ℃" means a residue obtained by drying the lignin derivative with a 100 ℃ air blower for 24 hours. The "form of a solution having 30% of nonvolatile components" and the "form of a solution having 10% of nonvolatile components" mean an aqueous solution having a concentration of nonvolatile components of the lignin derivatives of 28 to 32% and an aqueous solution having a concentration of nonvolatile components of the lignin derivatives of 8 to 12%, respectively.

The viscosity of the B-type is preferably 30 to 100 mPas, more preferably 35 to 90 mPas, and further preferably 40 to 80 mPas. When the B-type viscosity is within such a range, an appropriate viscosity can be imparted to the dispersed material, and the workability of the dispersed material slurry can be improved. The B-type viscosity is a value measured using a BL-type viscometer (Toyobo industries Co., Ltd.) at 20 ℃ and 60rpm using a No. 2 spindle.

The surface tension is preferably 25 to 55dyne/cm, more preferably 27 to 50dyne/cm, and still more preferably 29 to 45 dyne/cm. When the surface tension is in such a numerical range, the carrier has wettability to the dispersed material, and the state of the dispersed material slurry can be made good. The surface tension was measured by a surface tensiometer (CBVP-A3, manufactured by Kyowa Kagaku Co., Ltd.).

The conditions (1) to (2) can be adjusted by appropriately designing the reaction conditions of the lignosulfonic acid-based compound and the aromatic water-soluble compound. More specifically, the type or amount of the reaction initiator, the concentration of the reaction solution, the ratio of the lignosulfonic acid-based compound to the aromatic water-soluble compound, the type or amount of the side chain functional group of the aromatic water-soluble compound, the reaction temperature, the reaction time, and the like can be adjusted by appropriately changing the type or amount of the reaction initiator, the concentration of the reaction solution, the ratio of the lignosulfonic acid-based compound to the aromatic water-.

In other embodiments, other details regarding the lignin derivative are the same as those described in the composition (1), and the water-soluble compound is not limited to the aromatic water-soluble compound.

[4. dispersant (2) ]

The dispersant (2) of the present invention contains the above-mentioned composition (2), and can be used for various applications. Examples thereof include: dispersants for hydraulic compositions (for example, dispersants for cement and dispersants for gypsum), slurry dispersants for oil field excavation, dispersants for dyes, chelating agents, detergents, flocculants, thickeners, coating agents, paints, adhesives, and water-absorbent resins.

[4-1 ] dispersant (2) containing one embodiment of composition (2) ]

One embodiment of the composition (2) is a solid substance of a high-performance lignin derivative which can be used for dispersant applications and the like in construction sites of concrete and the like. Therefore, while recalculation of the moisture amount can be omitted at the construction site, a dedicated device is not required at the time of addition, contributing to improvement of workability. Accordingly, the dispersant (2) containing the composition (2) according to one embodiment is preferably a hydraulic composition dispersant or a slurry dispersant for oil field excavation, and is more preferably a hydraulic composition dispersant since ready-mixed concrete can be prepared by mixing with the hydraulic composition itself.

When the dispersant (2) of the present invention is used as a dispersant for muddy water for oilfield excavation, the muddy water for oilfield excavation is not particularly limited in composition as long as it is used as a muddy water for a fluid circulating in a well during the oilfield excavation operation and/or the recovery operation. The slurry for oilfield excavation can be generally classified into a water system and an oil system, and the water system slurry is preferable. The aqueous muddy water usually contains clay.

The pH of the slurry for oilfield excavation is not particularly limited, but is preferably 9 to 13, more preferably 9.5 to 11.5, and still more preferably about 11. The temperature of the slurry for oilfield excavation is not particularly limited, and may be a high temperature (for example, 80 ℃ or higher, preferably 90 ℃ or higher). The dispersant of the present invention is preferably added to the muddy water for oilfield excavation in an amount of 0.1 wt% or more, more preferably 0.5 wt% or more, based on the weight of the clay in the muddy water. The upper limit is preferably 30% by weight or less, more preferably 20% by weight or less.

The dispersant (2) of the present invention can also be used as a dye dispersant. Examples of the dye include: and a disperse dye used by dispersing an azo disperse dye such as c.i. disperse Red17 or an anthraquinone disperse dye such as c.i. disperse Red60 in a solvent. The material to be dyed is not particularly limited, and may be any of cloth and paper, and is preferably a material obtained by a high-temperature dyeing step (for example, 100 ℃ or higher, 110 ℃ or higher, and 120 ℃ or higher), and is preferably a synthetic fiber (for example, polyester, acetate, nylon).

The temperature condition in the high-temperature preliminary dyeing is not particularly limited, and the amount of the dispersant (2) of the present invention added to the dye is preferably 1% by weight or more, more preferably 5% by weight or more, based on the weight of the dye in the dye solution. The upper limit is preferably 100% by weight or less, more preferably 70% by weight or less. Dye compositions containing a dye and a dye dispersant are useful as inks and paints for dyeing various materials. The dye composition may contain any additives according to various uses.

When the dispersant (2) of the present invention is used as a dispersant for hydraulic compositions, the hydraulic compositions of the present invention can be constituted, and therefore, the following description will be made.

[ Hydraulic composition ]

The hydraulic composition of the present invention comprises a hydraulic material and the above-mentioned dispersant (2). The hydraulic material can be classified into a cement composition such as cement or gypsum and other hydraulic materials, and may be any of them. It should be noted that the concrete can be used as ready-mixed concrete without containing water.

The hydraulic composition may further contain fine aggregate (sand, etc.) or coarse aggregate (crushed stone, etc.) as required. Examples of the hydraulic material include: grout, mortar, concrete, stucco.

The details of the cement composition, gypsum composition and other additives are the same as those described in the above dispersant (1), and therefore, they are omitted.

[4-2 ] dispersant (2) of other embodiment containing composition (2) ]

The dispersed material dispersed by the dispersant (2) of another embodiment containing the above-mentioned composition (2) is not particularly limited, and examples thereof include: various organic or inorganic substances.

Examples of the organic substance include the following substances.

Organic pigments such as fast yellow, disazo orange, naphthol red, copper phthalocyanine pigments, phosphomolybdotungstate, tannate, Katanol (カタノール), Tamol rake (タモールレーキ), yellow-green isoindolinone (isoindolinone yellow greenish), yellow-red isoindolinone (isoindolinone yellow reddish), quinacridone, dioxazine violet, perinone orange, pyrene red, pyrene scarlet, pyrene red, pyrene brown red, and the like;

synthetic resins such as polycarbonate, polyvinyl chloride, polymethyl methacrylate, and fluorine resins;

and metal soaps such as aluminum stearate, zinc stearate, calcium stearate, magnesium stearate, zinc stearate-calcium stearate complex, lead stearate, cadmium stearate, barium stearate, calcium laurate, and zinc laurate.

The average particle diameter of the organic substance is generally 100 μm or less, preferably 0.1 to 50 μm. These organic substances may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Examples of the inorganic substance include the following substances.

Silicates such as kaolin, aluminum silicate, clay, talc, mica, calcium silicate, sericite, and bentonite;

carbonates such as calcium carbonate, magnesium carbonate, barium carbonate, and basic lead carbonate;

sulfates such as calcium sulfate and barium sulfate;

chromate salts such as strontium chromate and pigment yellow;

molybdates such as zinc molybdate, calcium molybdate, magnesium molybdate and the like;

metal oxides such as aluminum oxide, antimony oxide, titanium oxide, cobalt oxide, ferroferric oxide, iron sesquioxide, lead tetroxide, lead monoxide, chromium oxide green, tungsten trioxide, yttrium oxide, and the like;

metal hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, iron hydroxide, and metatitanic acid;

metal carbides such as silicon carbide, tungsten carbide, boron carbide, titanium carbide and the like;

aluminum nitride, silicon nitride, boron nitride, zirconium oxide, barium titanate, satin white, carbon black, graphite, chrome yellow, mercury sulfide, ultramarine, paris blue, titanium yellow, chrome vermilion, lithopone, copper acetoarsenite, nickel, silver, palladium, lead zirconate titanate, and the like.

The average particle diameter of the inorganic substance is generally 100 μm or less, preferably 0.1 to 50 μm. These inorganic substances may be used alone in 1 kind, or 2 or more kinds may be used in combination.

The shape of the dispersed material is not particularly limited, and examples thereof include: powder (powder), granule, fiber, plate, etc.

The dispersion medium that can be used when the dispersant (2) of the present invention is used to disperse a dispersion-target substance (for example, the above-mentioned organic substance and/or inorganic substance) is not particularly limited, and examples thereof include the following.

Water;

fuel oils such as kerosene, light oil, and kerosene (kerosene);

aliphatic hydrocarbons such as hexane, isohexane, cyclohexane, methylcyclohexane and isooctane;

aromatic hydrocarbons such as benzene, toluene, xylene, and cresol;

alcohols such as ethanol, methanol, isopropanol, butanol, pentanol, etc.;

esters such as ethyl acetate and dioctyl phthalate;

ethers such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, ethylene glycol monobutyl ether, carbitol, monoglyme, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, methyl cellosolve, and butyl cellosolve;

glycols such as ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, and hexylene glycol;

halogenated hydrocarbons such as 1,1, 1-trichloroethane, trichloroethylene, dichloroethylene, chlorodifluoromethane, etc.;

ketones such as methyl isoamyl ketone, methyl isobutyl ketone, acetone, methyl ethyl ketone and the like;

terpineol, liquid paraffin, mineral spirits, N- (2-hydroxyethyl) pyrrolidone, glycerol, and the like.

Among the above dispersion media, water is preferable. These dispersion media may be used alone in 1 kind, or 2 or more kinds may be used in combination.

[ method of Using other embodiment of dispersant (2) ]

The method of using the dispersant (2) of the present invention is not particularly limited. For example, the dispersant (2) of the present invention may be added after mixing the dispersant (2) with the dispersion medium, the dispersant (2) of the present invention may be added to the dispersion medium simultaneously or sequentially with the dispersant, or the dispersant (2) of the present invention may be added after mixing the dispersant with the dispersion medium in advance.

The amount of the dispersant (2) used in the present invention is not particularly limited, and may be appropriately adjusted depending on the kind or amount of the dispersion-target substance. As an example, the amount of the dispersion is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the dispersed material.

The amount of the dispersion medium used is usually 20 to 1,000 parts by weight per 100 parts by weight of the dispersed material.

The content of the lignin derivative as an active ingredient in the dispersant (2) of the present invention is preferably 25 to 100% by weight, more preferably 50 to 100% by weight, based on the total weight of the dispersant. In addition to the lignin derivative as an active ingredient in the present invention, other known additives may be added to the dispersant (2) of the present invention to such an extent that the object thereof is not impaired.

[ use of dispersant (2) ]

The dispersant (2) of the present invention can be used for various applications as described above. Examples thereof include: a dispersant for hydraulic compositions, a slurry dispersant for oil field excavation, a dye dispersant, a chelating agent, a cleaning agent, a flocculant, a thickener, a coating agent, a paint, an adhesive, a water-absorbent resin, and the like. Among these, dispersants for hydraulic compositions, slurry dispersants for oil field excavation, and dye dispersants are preferable, and dispersants for hydraulic compositions are more preferable.

[ dispersant for Hydraulic compositions ]

Hereinafter, the use of the dispersant of the present invention as a dispersant for hydraulic compositions will be described in detail.

The form of the dispersant for hydraulic compositions is not particularly limited. For example, it can be used in the form of an aqueous solution. When the dispersant of the present invention is used as a dispersant for a hydraulic composition, the dispersant may be previously blended with a cement composition containing no water, such as cement powder or dry mortar, to prepare a premix product for plastering, finishing of floor, grouting, or the like, or may be blended at the time of kneading the cement composition.

Examples of the dispersed material in the case where the dispersant of the present invention is used as a dispersant for a hydraulic composition include: various hydraulic materials. The hydraulic material can be classified into a cement composition such as cement or gypsum and other hydraulic materials, and may be any of them. The dispersant of the present invention can be used as a dispersant for hydraulic compositions, and can constitute hydraulic compositions together with the above hydraulic material and water. The hydraulic composition may further contain fine aggregate (sand, etc.) or coarse aggregate (crushed stone, etc.) as required. Examples of the hydraulic material include: grout, mortar, concrete, gypsum, stucco.

Examples

The present invention will be described in detail below with reference to examples. The following examples are examples for suitably illustrating the present invention, and do not limit the present invention. The measurement method of the physical property values and the like is the measurement method described above unless otherwise described. In the examples, "%" and "parts" represent% by weight and parts by weight, respectively, unless otherwise specified.

(embodiment mode 1)

[ thermal decomposition Point (. degree. C.) ]: the measurement was carried out by the following procedure using a thermogravimetric differential scanning calorimetry (TG-DTA) (trade name "STA 7200", manufactured by SII).

The granular composition or the target sample having a solid content of 10g was dried and solidified at 105 ℃. About 10mg of the solidified sample was heated from 50 ℃ to 600 ℃ at a heating rate of 10 ℃/min under a nitrogen atmosphere (nitrogen introduction amount: 100 mL/min). The temperature at which the weight reduction rate of the sample was extremely high was defined as the thermal decomposition point. The measurement was performed 3 times for each sample, and the average value was obtained.

In the case where the target sample was a polycarboxylic acid, the sample was dried and solidified at-20 ℃ for 1 day by a freeze dryer (trade name "FDU-1200", manufactured by Tokyo chemical and physical instruments Co., Ltd.), or at 105 ℃ for 1 day by an air blow dryer (trade name "air blow thermostat DKM 600", manufactured by Yamato scientific Co., Ltd.). In addition, the resultant was dried at 180 ℃ using a spray dryer (trade name "TR 120", PRECI).

[ thermogravimetric reduction (%) ]: the measurement was carried out by the following procedure using a thermogravimetric differential scanning calorimetry (TG-DTA) (trade name "STA 7200", manufactured by SII).

The granular composition or the target sample having a solid content of 10g was dried and solidified at 105 ℃. About 10mg of the solidified sample was heated from 50 ℃ to 600 ℃ at a heating rate of 10 ℃/min under a nitrogen atmosphere (nitrogen introduction amount: 100 mL/min). The weight loss of the sample up to 600 ℃ was taken as the thermogravimetric loss. The measurement was performed 3 times for each sample, and the average value was obtained.

[ weight average molecular weight ]: the measurement was carried out by Gel Permeation Chromatography (GPC) in terms of polyethylene glycol. The following describes the details of the GPC measurement conditions.

A measuring device; tosoh system

The column used; shodex Column OH-pak SB-806HQ, SB-804HQ, SB-802.5HQ

Eluting the solution; 0.05mM sodium nitrate/acetonitrile 8/2(v/v)

A standard substance; polyethylene glycol (manufactured by Tosoh or GL SCIENCE)

A detector; differential refractometer (Tosoh system)

Examples 1 to 1: preparation of granular composition (1)

A glass reaction vessel equipped with a thermometer, a stirrer, a reflux unit and a dropping unit was charged with 229g of water, 92g of poly (ethylene oxide) monophenyl ether (EO addition molar number: 50), 60g of Sunflow RH (lignosulfonate, manufactured by Nippon paper Co., Ltd.), 13g of 37% aqueous formaldehyde solution, 55g of 72% aqueous sulfuric acid solution and 0.05g of antifoam Pronal 753 (manufactured by Toho chemical Co., Ltd.), and the temperature of the reaction vessel was raised to 105 ℃ with stirring. The reaction was completed at a liquid temperature of 105 ℃ for 14 hours. After the reaction was completed, the temperature of the reaction mixture was lowered to 90 ℃ and 93g of 250g/L aqueous calcium hydroxide solution and 24g of 31% aqueous sodium hydroxide solution were added to the reaction vessel and stirred for further 1 hour. The gypsum generated by the neutralization was removed by filtering these mixtures, thereby obtaining a lignin derivative containing a copolymer having a weight average molecular weight of 41,300. The reaction weight ratio of the lignosulfonic acid-based compound [ L ] to the water-soluble compound [ M ] was [ L ]/[ M ] =39/61, and the reaction rate of the water-soluble compound was 95%. The lignin derivative was dried at 180 ℃ using a spray dryer (trade name "TR 120", manufactured by PRECI) to obtain a granular composition (1) of the present invention as a solid.

The granular composition (1) had a thermal decomposition point of 395 ℃ and a thermogravimetric reduction of 68%.

Examples 1 to 2: preparation of granular composition (2)

A glass reaction vessel equipped with a thermometer, a stirrer, a reflux unit and a dropping unit was charged with 275g of water, 69g of poly (ethylene oxide) monophenyl ether (EO addition molar number: 50), 150g of Sunflow RH (lignosulfonate, manufactured by Nippon paper Co., Ltd.), 12g of 37% aqueous formaldehyde solution, 40g of 72% aqueous sulfuric acid solution and 0.05g of Pronal 753 (manufactured by Toho chemical Co., Ltd.), and the temperature of the reaction vessel was raised to 105 ℃ with stirring. The reaction was completed at a liquid temperature of 105 ℃ for 10 hours. After the reaction liquid was cooled, 85g of 250g/L aqueous calcium hydroxide solution was added to the reaction vessel. The gypsum generated by neutralization was removed by filtering these mixtures, thereby obtaining a lignin derivative containing a copolymer having a weight average molecular weight of 22,800. The reaction weight ratio of the lignosulfonic acid-based compound [ L ] to the water-soluble compound [ M ] was [ L ]/[ M ] =68/32, and the reaction rate of the water-soluble compound was 89%. The lignin derivative was dried at 180 ℃ using a spray dryer (trade name "TR 120", manufactured by PRECI) to obtain a granular composition (2) of the present invention as a solid.

The granular composition (2) had a thermal decomposition point of 390 ℃ and a thermogravimetric reduction of 68%.

Examples 1 to 3: preparation of granular composition (3)

A granular composition (3) of the present invention was obtained as a solid by mixing 175g (in this case) of lignin sulfonic acid (trade name "Sunflow RH", manufactured by Nippon paper-making Co., Ltd.) in an amount of 70g of a solid content and 120g (trade name "SF-500R", manufactured by Flowric) of a polycarboxylic acid-based dispersant (trade name "TR 120", manufactured by PRECI Co., Ltd.) in an amount of 30g of a solid content, and drying the mixture at 180 ℃.

The weight ratio of the lignosulfonic acid-based compound [ L ] to the water-soluble compound [ M ] is [ L ]/[ M ] = 70/30.

The granular composition (3) had a thermal decomposition point of 236 ℃ and a thermogravimetric reduction of 65%.

Comparative examples 1 to 1: preparation of control sample (1) ]

Naphthalene sulfonic acid (trade name "Sunflow PS", manufactured by PRECI) was dried at 180 ℃ using a spray dryer (trade name "TR 120", manufactured by PRECI), and a control sample (1) was obtained as a solid.

The thermal decomposition point of the control sample (1) was 495 ℃ and the thermogravimetric reduction rate was 20%.

Comparative examples 1 to 2: preparation of control sample (2) ]

733 parts of water was charged into a glass reaction vessel equipped with a thermometer, a stirring device, a reflux device, a nitrogen introduction tube and a dropping device, the reaction vessel was replaced with nitrogen under stirring, and the temperature was raised to 100 ℃ under a nitrogen atmosphere. Then, a mixture of an aqueous monomer solution in which 21 parts of methacrylic acid, 30 parts of acrylic acid, 92 parts of methoxypolyethylene glycol methacrylate (the average molar number of addition of ethylene oxide is 25), 70 parts of water, and 3 parts of ammonium persulfate and 87 parts of water were mixed was continuously dropped into a reaction vessel maintained at 50 ℃ for 2 hours. Further, an aqueous solution of the polycarboxylic acid-based dispersant obtained by the reaction at 50 ℃ for 1 hour was adjusted to pH7 with a 31% NaOH aqueous solution. The weight-average molecular weight of the polycarboxylic acid-based dispersant in the solution was 18,300 (Mw/Mn was 1.6). The polycarboxylic acid-based dispersant was dried at-20 ℃ using a freeze dryer (trade name "FDU-1200", manufactured by Tokyo physical and chemical instruments Co., Ltd.), and a control sample (2) was obtained as a solid. The control sample (2) had a thermal decomposition point of 405 ℃ and a thermogravimetric reduction of 85%.

Comparative examples 1 to 3: preparation of control sample (3) ]

A polycarboxylic acid-based dispersant (trade name "SF-500R", manufactured by Flowric) was dried at 105 ℃ for 1 day using a dryer (trade name "forced air thermostat DKM 600", manufactured by Yamato scientific Co., Ltd.) to obtain a control sample (3) as a solid.

The control sample (3) had a thermal decomposition point of 335 ℃ and a thermogravimetric reduction of 88%.

Comparative examples 1 to 4: preparation of control sample (4) ]

Lignosulfonic acid (trade name "Sunflow RH", manufactured by Nippon paper-making Co., Ltd.) was dried at 180 ℃ using a spray dryer (trade name "TR 120", manufactured by PRECI Co., Ltd.) to obtain a control sample (4) as a solid.

The control sample (4) had a thermal decomposition point of 310 ℃ and a thermogravimetric reduction of 47%.

< concrete test >

Concrete (cement composition, hydraulic composition) to which the granular compositions of examples 1-1 to 3 and comparative examples 1-1 to 4 or the control samples were added was prepared by the following procedure, and the obtained concrete was subjected to slump test.

< procedure and evaluation method of concrete test: examples 1-1 to 3 and comparative examples 1-1 to 4>

The coarse aggregate, fine aggregate and cement blended as shown in Table 1 were charged under a high temperature environment (40 ℃ C.) in summer, and kneaded for 10 seconds by mechanical kneading with a forced twin-screw mixer. Next, water and the granular composition shown in Table 2 or a control sample (initial addition) were added in the amounts shown in Table 2, kneaded for 90 seconds, and then a part of the concrete was discharged, and a fresh concrete test (slump test JIS A1101 (measuring the spread of fresh concrete as a fluidity value) was performed to evaluate the initial concrete. furthermore, the prepared concrete was left to stand in a high temperature environment (40 ℃) for a predetermined time, and then the fresh concrete test was performed (after 15 minutes, 30 minutes, or 45 minutes) and the results are shown in Table 2.

[ Table 1]

The details of the symbols in table 1 are as follows.

C: mixing the following 3 kinds of cement by equal weight

Ordinary Portland Cement (made by Mitsubishi Cement of Utsubishi corporation, 3.16)

Ordinary Portland Cement (manufactured by Pacific Cement Co., Ltd., specific gravity of 3.16)

Ordinary portland cement (manufactured by Tokuyama, specific gravity 3.16)

W: tap water

S1: crushed lime sand produced by Dafen county jin Jiu (fine aggregate, specific gravity 2.66)

S2: crushed gravel sand produced in Zhou-nan province of Shankou county (fine aggregate, specific gravity of 2.66)

G1, G2: mountain county rock stone (coarse aggregate, specific gravity 2.73(G1), 2.66(G2))

[ Table 2]

In table 2, the numerical values of the added amounts are the solid content weight (%) of each granular composition or control sample with respect to the cement weight.

The following can be illustrated from table 2. The weight loss rate of the granular compositions (1) to (3) was 65% or 68%, the heat resistance was good, and the dispersibility was excellent in a high-temperature environment of 40 ℃ in summer (see examples 1-1 to 3). In particular, the granular composition further containing a lignin derivative has a thermal decomposition point of 395 ℃ and 390 ℃ and can improve heat resistance without causing a decrease in dispersibility due to resinification (see examples 1-1 and 2).

On the other hand, the control samples (1) to (4) obtained by solidifying a known dispersant had a reduced thermogravimetric decrease rate of 20% or 47%, which resulted in a decrease in dispersibility due to inevitable impurities (see comparative examples 1-1 and 4), or an excessively high thermogravimetric decrease rate of 85% or 88%, resulting in poor heat resistance (see comparative examples 1-2 and 3). Further, the thermal decomposition point was as low as 310 ℃ or 335 ℃ and the heat resistance was poor (see comparative examples 1-3 and 4), or as high as 405 ℃ or 495 ℃ and the dispersibility was poor due to resinification (see comparative examples 1-1 and 2).

(embodiment mode 2)

[ particle size distribution ]: the molecular weight distribution obtained by measuring 3g of each powder sample under dry conditions with a laser diffraction particle size distribution measuring apparatus (Mastersizer 3000 (Malvern), where the horizontal axis represents the particle size (μm) and the vertical axis represents the volume (%).

[ average particle diameter (μm) ]: the particle size distribution was determined by the average particle size at a cumulative area of 50%.

[ tapped apparent specific gravity (g/mL) ]: the granular composition is collected in a graduated tube (20 mL capacity) in an amount of 10 to 15 g. The test tube was placed in a specific volume tester (manufactured by Shishan scientific machine) and vibrated 50 times (40 rpm) at a drop height of 5cm, and the volume of the test tube was measured. Then, the tap apparent specific gravity was calculated by substituting the measurement result into the following equation.

The formula: tap apparent specific gravity (g/mL) = mass (g) of granular composition/volume (mL) of test tube after vibration

[ preparation example 1: preparation of granular composition (1)

A glass reaction vessel equipped with a thermometer, a stirrer, a reflux unit and a dropping unit was charged with 229g of water, 92g of poly (ethylene oxide) monophenyl ether (EO addition molar number: 50), 60g of Sunflow RH (lignosulfonate, manufactured by Nippon paper Co., Ltd.), 13g of 37% aqueous formaldehyde solution, 55g of 72% aqueous sulfuric acid solution and 0.05g of antifoam Pronal 753 (manufactured by Toho chemical Co., Ltd.), and the temperature of the reaction vessel was raised to 105 ℃ with stirring. The reaction was completed at a liquid temperature of 105 ℃ for 14 hours. After the reaction was completed, the temperature of the reaction mixture was lowered to 90 ℃ and 93g of 250g/L aqueous calcium hydroxide solution and 24g of 31% aqueous sodium hydroxide solution were added to the reaction vessel and further stirred for 1 hour. The gypsum generated by the neutralization was removed by filtering these mixtures, whereby lignin derivative (2-1) composed of a copolymer having a weight average molecular weight of 41,300 was obtained in the form of an aqueous solution.

The lignin derivative (2-1) was dried at 180 ℃ using a spray dryer (trade name "TR 120", manufactured by PRECI Co., Ltd.) to obtain a granular composition (1) of the present invention as a solid. A graph showing the particle size distribution of the resulting granular composition (1) is shown in fig. 1. The weight ratio of the reaction between the lignosulfonic acid-based compound [ L ] and the aromatic water-soluble compound [ M ] was [ L ]/[ M ] =39/61, and the reaction rate of the aromatic water-soluble compound was 95%.

[ preparation example 2: preparation of granular composition (2)

A glass reaction vessel equipped with a thermometer, a stirrer, a reflux unit and a dropping unit was charged with 275g of water, 69g of poly (ethylene oxide) monophenyl ether (EO addition molar number: 50), 150g of Sunflow RH (lignosulfonate, manufactured by Nippon paper Co., Ltd.), 12g of 37% aqueous formaldehyde solution, 40g of 72% aqueous sulfuric acid solution and 0.05g of Pronal 753 (manufactured by Toho chemical Co., Ltd.), and the temperature of the reaction vessel was raised to 105 ℃ with stirring. The reaction was completed at a liquid temperature of 105 ℃ for 10 hours. After the reaction liquid was cooled, 85g of 250g/L aqueous calcium hydroxide solution was added to the reaction vessel. The gypsum generated by the neutralization was removed by filtering these mixtures, and thereby lignin derivative (2-2) composed of a copolymer having a weight average molecular weight of 22,800 was obtained in the form of an aqueous solution.

The lignin derivative (2-2) was dried at 180 ℃ using a spray dryer (trade name "TR 120", manufactured by PRECI Co., Ltd.) to obtain a granular composition (2) of the present invention as a solid. A graph showing the particle size distribution of the resulting granular composition (2) is shown in fig. 2. The weight ratio of the reaction between the lignosulfonic acid-based compound [ L ] and the aromatic water-soluble compound [ M ] was [ L ]/[ M ] =68/32, and the reaction rate of the aromatic water-soluble compound was 89%.

[ example 2-1]

The granular composition (1) prepared in preparation example 1 was used.

[ examples 2-2]

The granular composition (2) prepared in preparation example 2 was used.

Comparative example 2-1

As a conventional lignin-based dispersant (a), Sunflow RH (modified lignin sulfonic acid-based compound, manufactured by japan paper-making corporation) was used. A graph showing the particle size distribution of Sunflow RH is shown in fig. 3.

The values of the average particle diameter, the cumulative area of the particle diameter of 100 μm or less in the particle size distribution, and the tap apparent specific gravity obtained from the particle size distributions shown in FIGS. 1 to 3 are shown in Table 3.

[ Table 3]

Examples 2-3 to 4, comparative example 2-2 and reference examples 2-1 to 2: dispersant test)

The cement compositions (mortars) of the samples to which the aqueous solutions of examples 2-1 to 2 and comparative example 2-1 and the aqueous solution of the lignin derivative (2-1) and the aqueous solution of the lignin derivative (2-2) were added were prepared by the following procedure. Sand, cement and water blended as shown in table 4 (W/C =45%) and the respective samples in the amounts shown in table 5 were put into a forced twin-shaft mixer at ambient temperature (20 ℃) and kneaded for 90 seconds by mechanical kneading with the forced twin-shaft mixer, thereby obtaining cement compositions. In the case of the powdery samples, a small amount of water as shown in table 4 was previously collected, and after mixing cement, sand, and each sample (premixing), water was added. With respect to the obtained cement composition, slump test was conducted in accordance with the following procedure. The evaluation results are also shown in Table 5.

[ slump test ]: the measurement was carried out in accordance with JIS A1101 (the slump value was determined as the falling distance from the apex of the freshly mixed cement composition, and the fluidity value was determined as the spread). The elapsed time is the elapsed time immediately after the discharge from the forced twin-shaft mixer.

[ Table 4]

Footnotes of Table 4

C: mixing the following 3 kinds of materials in equal amount

Ordinary portland cement (manufactured by Tokuyama, specific gravity 3.16)

W: tap water

S: mountain sand produced in Kangchuan province (fine aggregate, specific gravity 2.57)

[ Table 5]

Footnotes of Table 5

The addition amount (weight percent) is as follows: the amount of the cement dispersant added to 100% by weight of the solid content of the cement composition

SL: slump value (cm)

The following is illustrated in table 5. When the granular composition (1) or (2) of the present invention was used, the slump values immediately after the addition, 15 minutes, 30 minutes and 60 minutes were about 220cm, about 195cm, about 165cm and about 123cm, respectively, and the dispersibility of the hydraulic material was maintained (see examples 2 to 3 and 4). On the other hand, when the conventional lignosulfonic acid-based dispersant was added in the form of powder, although the slump value immediately after the addition was 192cm, the dispersibility of the hydraulic material was observed, the slump value after 15 minutes was 110cm, and the dispersibility of the hydraulic material was significantly deteriorated (see comparative example 2-2).

When the lignin derivative was added in a liquid state as an aqueous solution thereof, instead of being dried to prepare a granular composition, the slump value immediately after the addition was about 193cm, and the dispersibility of the hydraulic material was observed, but the slump value after 15 minutes was about 102.5cm, and the dispersibility of the hydraulic material was remarkably deteriorated (see reference examples 2-1 to 2).

From the above results, the granular composition of the present invention exhibits better dispersibility than the conventional lignosulfonic acid-based dispersant, and when used in the form of a powder, not only the initial dispersibility but also the dispersibility over time can be improved.

(embodiment mode 3)

Example 3-1 preparation of Lignin derivative (1)

A glass reaction vessel equipped with a thermometer, a stirrer, a reflux unit and a dropping unit was charged with 236g of water, 92g of poly (ethylene oxide) monophenyl ether (EO addition molar number: 100), 5g of p-hydroxybenzoic acid, 11g of aminobenzenesulfonic acid, 60g of Sunflow RH (lignosulfonate, manufactured by Nippon paper Co., Ltd.), 13g of 37% aqueous formaldehyde solution, 55g of 72% aqueous sulfuric acid solution and 0.05g of Pronal 753 (manufactured by Toho chemical Co., Ltd.), and the temperature of the reaction vessel was raised to 105 ℃ with stirring. The reaction was completed at a liquid temperature of 105 ℃ for 10 hours. After the reaction was completed, 93g of 250g/L aqueous calcium hydroxide solution and 24g of 31% aqueous sodium hydroxide solution were added to the reaction vessel, and the mixture was further stirred for 1 hour. The gypsum generated by neutralization was removed by filtering the mixture, and a liquid material containing lignin derivative (1) of a copolymer having a weight average molecular weight of 45,300 was obtained.

Example 3-2 preparation of Lignin derivative (2)

A glass reaction vessel equipped with a thermometer, a stirrer, a reflux unit and a dropping unit was charged with 229g of water, 92g of poly (ethylene oxide) monophenyl ether (EO addition molar number: 50), 60g of Sunflow RH (lignosulfonate, manufactured by Nippon paper Co., Ltd.), 13g of 37% aqueous formaldehyde solution, 55g of 72% aqueous sulfuric acid solution and 0.05g of antifoam Pronal 753 (manufactured by Toho chemical Co., Ltd.), and the temperature of the reaction vessel was raised to 105 ℃ with stirring. The reaction was completed at a liquid temperature of 105 ℃ for 14 hours. After the reaction was completed, the temperature of the reaction mixture was lowered to 90 ℃ and 93g of 250g/L aqueous calcium hydroxide solution and 24g of 31% aqueous sodium hydroxide solution were added to the reaction vessel and stirred for further 1 hour. The gypsum generated by neutralization was removed by filtering the mixture, and a liquid substance containing the lignin derivative (2) of the copolymer having a weight average molecular weight of 41,300 was obtained.

Examples 3 to 3 preparation of Lignin derivative (3)

A glass reaction vessel equipped with a thermometer, a stirrer, a reflux unit and a dropping unit was charged with 283g of water, 92g of poly (ethylene oxide) monophenyl ether (EO addition molar number: 25), 80g of Sunflow RH (lignosulfonate, manufactured by Nippon paper Co., Ltd.), 12g of 37% aqueous formaldehyde solution, 72g of 72% aqueous sulfuric acid solution and 0.05g of Pronal 753 (manufactured by Toho chemical Co., Ltd.), and the temperature of the reaction vessel was raised to 105 ℃ with stirring. The reaction was completed at a liquid temperature of 105 ℃ for 10 hours. After the reaction liquid was cooled, 95g of 250g/L aqueous calcium hydroxide solution and 25g of 31% aqueous sodium hydroxide solution were added to the reaction vessel. The gypsum generated by neutralization was removed by filtering the mixture, and a liquid substance containing the lignin derivative (3) of the copolymer having a weight average molecular weight of 26,900 was obtained.

Examples 3 to 4 preparation of Lignin derivative (4)

A glass reaction vessel equipped with a thermometer, a stirrer, a reflux unit and a dropping unit was charged with 229g of water, 92g of poly (oxypropylene) monophenyl ether (PO addition mol number: 130), 22g of Sunflow RH (lignosulfonate, manufactured by Nippon paper Co., Ltd.), 10g of p-hydroxybenzoic acid, 13g of 37% aqueous formaldehyde solution, 55g of 72% aqueous sulfuric acid solution and 0.05g of Pronal 753 (manufactured by Toho chemical Co., Ltd.), and the temperature of the reaction vessel was raised to 105 ℃ with stirring. The reaction was completed at a liquid temperature of 105 ℃ for 14 hours. After the reaction was completed, the temperature of the reaction product was lowered to 90 ℃, 54g of a 31% aqueous sodium hydroxide solution was added to the reaction vessel, and the mixture was further stirred for 1 hour. The gypsum generated by neutralization was removed by filtering the mixture, and a liquid substance containing the lignin derivative (4) of the copolymer having a weight average molecular weight of 21,200 was obtained.

Examples 3 to 5 preparation of Lignin derivative (5)

A glass reaction vessel equipped with a thermometer, a stirrer, a reflux unit and a dropping unit was charged with 229g of water, 92g of poly (ethylene oxide) monophenyl ether (EO addition molar number: 50), 60g of Pearlex NP (lignosulfonate, manufactured by Nippon paper Co., Ltd.), 13g of 37% aqueous formaldehyde solution, 55g of 72% aqueous sulfuric acid solution and 0.05g of antifoamer Pronal 753 (manufactured by Toho chemical Co., Ltd.), and the temperature of the reaction vessel was raised to 105 ℃ with stirring. The reaction was completed at a liquid temperature of 105 ℃ for 3 hours. After completion of the reaction, 72g of 250g/L calcium hydroxide aqueous solution and 24g of 31% sodium hydroxide aqueous solution were added to the reaction vessel, and further stirred for 1 hour. The gypsum generated by neutralization was removed by filtering the mixture, and a liquid substance containing the lignin derivative (5) of the copolymer having a weight average molecular weight of 39,700 was obtained.

Examples 3 to 6 preparation of Lignin derivative (6)

A glass reaction vessel equipped with a thermometer, a stirrer, a reflux unit and a dropping unit was charged with 229g of water, 82g of poly (ethylene oxide) monophenyl ether (EO addition molar number: 50), 70g of Sunflow RH (lignosulfonate, manufactured by Nippon paper Co., Ltd.), 13g of 37% aqueous formaldehyde solution, 55g of 72% aqueous sulfuric acid solution and 0.05g of antifoam Pronal 753 (manufactured by Toho chemical Co., Ltd.), and the reaction vessel was heated to 120 ℃ under pressure with stirring. The reaction was completed at a liquid temperature of 120 ℃ for 2 hours. After the reaction was completed, the temperature of the reaction mixture was lowered to 50 ℃ and 93g of 250g/L aqueous calcium hydroxide solution and 24g of 31% aqueous sodium hydroxide solution were added to the reaction vessel and stirred for a further 2 hours. The gypsum generated by neutralization was removed by filtering the mixture, and a liquid substance containing the lignin derivative (6) of the copolymer having a weight average molecular weight of 34,400 was obtained.

Examples 3 to 7 preparation of Lignin derivative (7)

A glass reaction vessel equipped with a thermometer, a stirrer, a reflux unit and a dropping unit was charged with 229g of water, 122g of poly (oxyethylene) monophenyl ether (EO addition mol number: 70), 20g of Vanillex HW (lignosulfonate, manufactured by Nippon paper Co., Ltd.), 5g of p-hydroxybenzoic acid, 13g of 37% aqueous formaldehyde solution, 58g of 72% aqueous sulfuric acid solution and 0.05g of antifoam Pronal 753 (manufactured by Toho chemical Co., Ltd.), and the temperature of the reaction vessel was raised to 105 ℃ with stirring. The reaction was completed at a liquid temperature of 105 ℃ for 14 hours. After completion of the reaction, 62g of 250g/L calcium hydroxide aqueous solution and 39g of 31% sodium hydroxide aqueous solution were added to the reaction vessel, and further stirred for 1 hour. The gypsum generated by neutralization was removed by filtering the mixture, and a liquid material containing the lignin derivative (7) of the copolymer having a weight average molecular weight of 16,800 was obtained.

Examples 3 to 8 preparation of Lignin derivative (8)

A glass reaction vessel equipped with a thermometer, a stirring device, a reflux device and a dropping device was charged with 192g of water, 52g of poly (ethylene oxide) monophenyl ether (EO addition mol number: 70), 35g of Sunflow RH (lignosulfonate, manufactured by Nippon paper Co., Ltd.), 10g of aminobenzenesulfonic acid, 11g of 37% aqueous formaldehyde solution, 55g of 72% aqueous sulfuric acid solution and 0.05g of antifoamer Pronal 753 (manufactured by Toho chemical Co., Ltd.), and the reaction vessel was heated to 105 ℃ with stirring. The reaction was completed at a liquid temperature of 105 ℃ for 14 hours. After completion of the reaction, 90g of 250g/L calcium hydroxide aqueous solution and 24g of 31% sodium hydroxide aqueous solution were added to the reaction vessel, and further stirred for 1 hour. The gypsum generated by neutralization was removed by filtering the mixture, and a liquid material containing the lignin derivative (8) of the copolymer having a weight average molecular weight of 29,900 was obtained.

Examples 3 to 9 preparation of Lignin derivative (9)

A glass reaction vessel equipped with a thermometer, a stirrer, a reflux unit and a dropping unit was charged with 229g of water, 43g of poly (ethylene oxide) monophenyl ether (EO addition molar number: 25), 10g of naphthalene, 90g of SunEkis M (lignosulfonate, manufactured by Nippon paper Co., Ltd.), 21g of 37% aqueous formaldehyde solution, 77g of 72% aqueous sulfuric acid solution and 0.05g of Pronal 753 (manufactured by Toho chemical Co., Ltd.), and the temperature of the reaction vessel was raised to 105 ℃ with stirring. The reaction was completed at a liquid temperature of 105 ℃ for 8 hours. After the reaction was completed, 52g of 250g/L calcium hydroxide aqueous solution and 34g of 31% sodium hydroxide aqueous solution were added to the reaction vessel, and further stirred for 2 hours. The gypsum generated by neutralization was removed by filtering the mixture, and a liquid substance containing the lignin derivative (9) of the copolymer having a weight average molecular weight of 18,300 was obtained.

Examples 3 to 10 preparation of Lignin derivative (10)

A glass reaction vessel equipped with a thermometer, a stirrer, a reflux unit and a dropping unit was charged with 229g of water, 92g of poly (ethylene oxide) monophenyl ether (EO addition mol number: 70), 57g of Sunflow RH (lignosulfonate, manufactured by Nippon paper Co., Ltd.), 13g of 37% aqueous formaldehyde solution, 55g of 72% aqueous sulfuric acid solution and 0.05g of antifoam Pronal 753 (manufactured by Toho chemical Co., Ltd.), and the temperature of the reaction vessel was raised to 105 ℃ with stirring. The polymerization was completed at a liquid temperature of 105 ℃ for 14 hours. After the reaction was completed, the temperature of the reaction mixture was lowered to 90 ℃ and 97g of a 250g/L aqueous calcium hydroxide solution and 19g of a 31% aqueous sodium hydroxide solution were added to the reaction vessel and stirred for further 30 minutes. The gypsum generated by neutralization was removed by filtering the mixture, and a liquid substance containing the lignin derivative (10) of the copolymer having a weight average molecular weight of 29,300 was obtained.

Comparative example 3-1 Lignin-based dispersant (a)

As a conventional lignin-based dispersant (a), Sunflow RH (modified lignin sulfonic acid-based compound, manufactured by japan paper-making corporation) was used.

Comparative examples 3-2 preparation of Lignin derivative (b)

According to the description of Japanese patent application laid-open No. 2008-514402, a glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen introduction tube and a dropping device was charged with 98.7g of water, 152.4g of polyethylene glycol mono (3-methyl-3-butenyl) ether (the average molar number of addition of ethylene oxide is 50), 0.3g of acrylic acid and 2.1g of kraft lignin (product number: 37095-9, manufactured by Sigma-Aldrich Co.) and the reaction vessel was nitrogen-substituted under stirring and heated to 58 ℃ under a nitrogen atmosphere. After the liquid temperature reached 58 ℃, an aqueous solution obtained by diluting 0.5g of a 30% aqueous hydrogen peroxide solution with 6.3g of water was added, and immediately, dropwise addition of an aqueous monomer solution obtained by diluting 9.2g of acrylic acid with 21.5g of water and 32.6g of an aqueous chain transfer agent solution in which 0.2g of L-ascorbic acid and 0.4g of 3-mercaptopropionic acid as a chain transfer agent were mixed was started. The aqueous monomer solution was added dropwise over 3 hours, and the aqueous chain transfer agent solution was added dropwise over 3 hours and 30 minutes. After the completion of the dropwise addition of the aqueous chain transfer agent solution, the temperature was maintained at 58 ℃ for 2 hours to obtain a liquid material of lignin derivative (b) containing an aqueous copolymer solution having a weight average molecular weight of 33,000.

Comparative examples 3 to 3 preparation of aromatic Water-soluble Compound homopolymer (c)

An aromatic water-soluble compound homopolymer (c) was obtained as an aqueous solution of a copolymer having a weight-average molecular weight of 31,800 by exactly the same operation except that Sunflow RH was not used in example 1. The reaction rate of the aromatic water-soluble compound was 95%.

Comparative examples 3 to 4 naphthalenesulfonic acid dispersants (d)

As the naphthalenesulfonic acid-based dispersant (d), Sunflow PS (naphthalenesulfonic acid-formaldehyde condensate, manufactured by japan paper-making corporation) was used.

Comparative examples 3 to 5 and 6 polycarboxylic acid-based dispersants (e) (f)

As the polycarboxylic acid-based dispersant (e), commercially available Flowric SF-500S (manufactured by Flowric corporation) was used, and as the polycarboxylic acid-based dispersant (f), commercially available Flowric SF-500R (manufactured by Flowric corporation) was used.

Comparative examples 3 to 7 preparation of Lignin derivative (11)

A glass reaction vessel equipped with a thermometer, a stirrer, a reflux unit and a dropping unit was charged with 229g of water, 92g of poly (ethylene oxide) monophenyl ether (EO addition molar number: 50), 59g of Sunflow RH (lignosulfonate, manufactured by Nippon paper Co., Ltd.), 13g of 37% aqueous formaldehyde solution, 20g of 72% aqueous sulfuric acid solution and 0.05g of Pronal 753 (manufactured by Toho chemical Co., Ltd.), and the temperature of the reaction vessel was raised to 105 ℃ with stirring. The polymerization was completed at a liquid temperature of 105 ℃ for 6 hours. After the reaction was completed, the temperature of the reaction product was lowered to 90 ℃ and 35g of 250g/L aqueous calcium hydroxide solution and 10g of 31% aqueous sodium hydroxide solution were added to the reaction vessel and stirred for further 30 minutes. The gypsum generated by neutralization was removed by filtering the mixture, and a liquid material containing the lignin derivative (11) of the copolymer having a weight average molecular weight of 18,200 was obtained.

Comparative examples 3 to 8 preparation of Lignin derivative (12)

A glass reaction vessel equipped with a thermometer, a stirrer, a reflux unit and a dropping unit was charged with 208g of water, 126g of poly (ethylene oxide) monophenyl ether (EO addition molar number: 50), 14g of Sunflow RH (lignosulfonate, manufactured by Nippon paper Co., Ltd.), 10g of 37% aqueous formaldehyde solution, 41g of 72% aqueous sulfuric acid solution and 0.05g of Pronal 753 (manufactured by Toho chemical Co., Ltd.), and the temperature of the reaction vessel was raised to 105 ℃ with stirring. The polymerization was completed at a liquid temperature of 105 ℃ for 14 hours. After the reaction was completed, the temperature of the reaction mixture was lowered to 90 ℃ and 97g of a 250g/L aqueous calcium hydroxide solution and 19g of a 31% aqueous sodium hydroxide solution were added to the reaction vessel and stirred for further 30 minutes. Gypsum generated by the neutralization was removed by filtering these mixtures, thereby obtaining an aqueous solution of lignin derivative (12) containing a copolymer having a weight average molecular weight of 30,900.

In Table 6, the lignin derivatives (1) to (10) obtained in examples 3-1 to 10, the lignin-based dispersant (a) of comparative example 3-1, the lignin derivative (B) obtained in comparative example 3-2, the aromatic water-soluble compound homopolymer (c) obtained in comparative example 3-3, the naphthalenesulfonic acid-based dispersant of comparative example 3-4, the polycarboxylic acid-based dispersants of comparative examples 3-5 and 6, and the lignin derivatives (11) to (12) obtained in comparative examples 3-7 to 8 were each represented by the weight ratio ([ L ]/[ M ]) of the reaction between the aromatic water-soluble compound and the lignosulfonic acid-based compound [ L ] used, the reaction rate (%) of the aromatic water-soluble compound, and the B-type viscosity (mPas) in the form of a solution in which the nonvolatile component at 100 ℃ was 30%, Surface tension (dyne/cm) in the form of a solution containing 10% of nonvolatile components at 100 ℃.

The measurement methods of the B-type viscosity and the surface tension are as follows.

[ viscosity (mPas) ]

Ion-exchanged water was added so that the nonvolatile components at 100 ℃ of the target sample were 30% in solution form, and 100g of the prepared solution was measured at 20 ℃ and 60rpm with a No. 2 spindle using a B-type viscometer (trade name: BL-type viscometer, manufactured by Toyobo industries, Ltd.).

[ surface tension (dyne/cm) ]

Ion-exchanged water was added to the sample so that the nonvolatile content of the sample at 100 ℃ was 10%, and 100g of the prepared solution was measured by a surface tensiometer (trade name "CBVP-A3", manufactured by Kyowa chemical Co., Ltd.).

[ Table 6]

Footnotes of Table 6

PEOPH 100: poly (oxyethylene) monophenyl ether (EO addition mole number: 100)

PEOPH 50: poly (oxyethylene) monophenyl ether (EO addition mole number: 50)

PEOPH 25: poly (oxyethylene) monophenyl ether (EO addition mole number: 25)

PEOPH 70: poly (oxyethylene) monophenyl ether (EO addition mole number: 70)

PPOPH 130: poly (oxypropylene) monophenyl ether (PO addition mol number: 130)

PHB: p-hydroxybenzoic acid

An ANS: aminobenzenesulfonic acid

NAP: naphthalene

(examples 3-11 to 20 and comparative examples 3-9 to 16: Cement composition test)

The cement compositions to which the samples of examples 3-1 to 10 and comparative examples 3-1 to 8 were added were prepared by the following procedure.

Each sample of the coarse aggregate, the fine aggregate, the cement and the water blended as shown in table 7 (W/C =45%) and the amount (converted into solid content) shown in table 8 was charged into a forced double-shaft mixer at ambient temperature (20 ℃), and kneaded for 90 seconds by mechanical kneading in the forced double-shaft mixer, thereby obtaining a cement composition (each sample was charged after being mixed into water). The obtained cement composition was subjected to slump test, air quantity measurement, and viscosity evaluation in the following manner.

[ slump test and air quantity measurement ]

Immediately after the cement composition was discharged from the forced twin-screw mixer, the following fresh cement composition was subjected to the following tests. The test results are shown in table 8.

Slump test: the slump value was determined in accordance with JIS A1101 (the slump value was determined as the falling distance from the apex of the freshly mixed cement composition, and the flow value was determined as the spread).

Air volume determination test: according to JIS A1128.

[ evaluation of viscosity of Cement composition ]

Sensory evaluation was performed by 5 evaluators, and evaluation was performed according to the following criteria.

< evaluation criteria for tackiness >

A: moderate viscosity was imparted to the cement composition, and little feathering was observed.

B: the cement composition was rendered viscous, but feathering was observed.

C: no tack was imparted to the cement composition and significant scumming was also observed.

[ Table 7]

Footnotes of Table 7

C: mixing the following 3 kinds of materials in equal amount

Ordinary portland cement (manufactured by Tokuyama, specific gravity 3.16)

W: tap water

S1: mountain sand produced in Kangchuan province (fine aggregate, specific gravity 2.57)

S2: garland produced lith (fine aggregate, specific gravity 2.61)

G: crushed stone produced by green plum (coarse aggregate, specific gravity 2.65)

[ Table 8]

Footnotes of Table 8

The addition rate (mass%): the addition rate of the cement dispersant to 100% by mass of the solid content of the cement composition

SL: slump value (cm)

The following is clear from table 8. When the flow values of mortars obtained using the lignin derivatives (1) to (10) and the polycarboxylic acid-based dispersant (e) are compared between the same addition rates, the slump values are substantially the same, and the slump value of some of the lignin derivatives is higher than that of the polycarboxylic acid-based dispersant (e). In addition, when the lignin-based dispersant (a) or the lignin derivative (b) to be compared was compared with the lignin derivatives (1) to (10), the latter showed a remarkably high slump value. From this, it is understood that the dispersant of the present invention containing a lignin derivative has high dispersibility, and the high dispersibility is exhibited because the number of moles of alkylene oxide added is 25 or more or the reaction rate of the aromatic water-soluble compound is high.

Further, when the lignin derivatives (2) of examples 3 to 12 were compared with the lignin derivatives (11) of comparative examples 3 to 15, it was found that the slump values of examples 3 to 12 were significantly high. The lignin derivative (2) showed performance because the lignin derivative of the present invention had a high reaction rate of 95% for the lignosulfonic acid-based compound and the aromatic water-soluble compound and a low reaction rate of 38% for the lignin derivative (11), and the lignin derivative had a viscosity and a surface tension within predetermined ranges because the lignosulfonic acid-based compound and the aromatic water-soluble monomer reacted at a high reaction rate.

Further, the lignin derivatives (1) to (10) were found to have a significantly reduced amount of air as compared with the conventional lignin dispersants (a), and to have a high air permeability which is a disadvantage of the lignin dispersants.

Further, it is found that lignin derivatives (1) to (10) can significantly improve the concrete viscosity as compared with the polycarboxylic acid water reducing agent (e) in addition to the conventional lignin dispersing agent (a), and are also superior in the state of concrete.

(examples 3-21 to 30, comparative examples 3-17 to 24: Gypsum composition test)

The samples of examples 3-1 to 10 and comparative examples 3-1 to 8 were compared for dispersibility in a gypsum composition. The dispersion fluidity and the hardening time of gypsum shown in Table 9 were evaluated as follows.

[ Dispersion fluidity (mm) of Gypsum Fibrosum ]

110g of a liquid (solvent: water) containing each sample in which the amount of solid matter described in Table 9 was added (wt% based on the gypsum composition) and 71.5g of Gypsum Fibrosum SK (Gentame chemical Co.) were mixed and stirred with a stirrer at 600rpm for 20 seconds. Immediately after pouring the slurry into a cylindrical tube for measuring fluidity (inner diameter: 40mm, height: 50mm) on a glass plate, the cylindrical tube was pulled out, and the fluidity value of the slurry at 2 points was measured, and the average value thereof was taken as the dispersion fluidity.

[ hardening time (min) of Gypsum Fibrosum ]

Using a vicat coagulation time measuring apparatus, the coagulation time was measured in accordance with JIS R9112: 2015 (physical test method for a ceramic ware model material using gypsum). The hardening time means the time until the gauge needle of the measuring instrument stops at a depth of 1mm from the surface of the test article.

[ type B viscosity (mPas) of Gypsum Fibrosum ]

A gypsum composition was prepared under the same test conditions as the above dispersion fluidity, and the viscosity of the gypsum immediately after stirring was measured using a B-type viscometer (BL type, Toyobo industries Co., Ltd.) at 20 ℃ and 60rpm using a No. 2 rotor or a No. 3 rotor.

[ Table 9]

As is clear from table 9, the lignin derivatives of the examples have an increased dispersion fluidity, a shorter curing time, and a reduced B-type viscosity as compared with the lignin-based dispersant (a). Further, the dispersant exhibited the same dispersion fluidity and the same curing time as those of the conventional naphthalenesulfonic acid dispersant (d), and the B-type viscosity was decreased. Further, the polycarboxylic acid dispersants (e) to (f) are inferior in dispersion fluidity, but the curing time is short and the B-type viscosity is also low. When compared with the lignin derivatives (11) to (12) of the comparative examples, the dispersion fluidity was increased, and the curing time was also shortened.

From the above results, it is understood that the lignin derivatives of the examples not only impart dispersibility to the gypsum composition with a small amount of addition, but also shorten the hardening time and reduce the viscosity of the gypsum composition. This characteristic contributes to an improvement in the production efficiency of the gypsum composition or an improvement in the filling property of the gypsum into the mold.

Claims

1. A composition comprising a lignosulfonic acid-based compound and a water-soluble compound.

2. The composition according to claim 1, wherein the composition has a thermogravimetric reduction rate of 50 to 80% as measured by a thermogravimetric differential thermal analysis apparatus, and is in the form of a particulate matter.

3. The composition according to claim 2, which has a thermal decomposition point of 350 ℃ or higher and lower than 400 ℃ as measured by a thermogravimetric differential thermal analyzer.

4. The composition of claim 2 or 3, further comprising a lignin derivative as a reactant of the lignosulfonic acid-based compound and the water-soluble compound.

5. The composition of claim 4, wherein the lignin derivative has anionic functional groups.

6. The composition according to claim 4 or 5, wherein the lignin derivative has a polyoxyalkylene hydrocarbon chain having an average molar number of addition of alkylene oxide of 25 or more.

7. The composition according to any one of claims 4 to 6, wherein the lignin derivative has a reaction weight ratio ([ L ]/[ M ]) of the lignosulfonic acid-based compound [ L ] to the water-soluble compound [ M ] of 1 to 99/99 to 1.

8. The composition according to any one of claims 2 to 7, wherein the water-soluble compound is an aromatic water-soluble compound.

9. The composition according to claim 8, wherein the aromatic water-soluble compound contains 1 or more selected from the group consisting of an aromatic water-soluble compound having a polyoxyalkylene chain, an aromatic water-soluble compound having a carboxyl group, and an aromatic water-soluble compound having a sulfo group.

10. The composition according to claim 8 or 9, which contains a lignin derivative having a reaction rate of 50% or more with respect to the aromatic water-soluble compound.

11. A dispersant comprising the composition of any one of claims 1 to 10.

12. The dispersant of claim 11, which is a slurry dispersant for oil field excavation or a dispersant for hydraulic compositions.

13. A composition comprising a lignin derivative as a reactant of a lignosulfonic acid-based compound and an aromatic water-soluble compound,

the lignin derivative satisfies the following conditions (A) to (B) and is a granular material, or

The lignin derivative satisfies the following conditions (1) to (2), and is a liquid material:

condition (a): the average particle diameter is in the range of 30 to 250 μm,

14. The composition of claim 13, which further satisfies the following condition (C) in the case where the composition is the pellet:

15. The composition of claim 13 or 14, wherein the lignin derivative has anionic functional groups.

16. The composition according to any one of claims 13 to 15, wherein the lignin derivative has a polyoxyalkylene chain having an average molar number of addition of alkylene oxide of 25 or more.

17. The composition according to any one of claims 13 to 16, wherein the lignin derivative has a reaction weight ratio ([ L ]/[ M ]) of the lignosulfonic acid-based compound [ L ] to the aromatic water-soluble compound [ M ] of 1 to 99/99 to 1.

18. The composition according to any one of claims 13 to 17, wherein the aromatic water-soluble compound contains 1 or more selected from an aromatic water-soluble compound having a polyoxyalkylene chain, an aromatic water-soluble compound having a carboxyl group, and an aromatic water-soluble compound having a sulfo group.

19. The composition according to any one of claims 13 to 18, which contains a lignin derivative having a reaction rate of 50% or more with respect to the aromatic water-soluble compound.

20. A dispersant comprising the composition of any one of claims 13 to 19.

21. The dispersant according to claim 20, which is a dispersant for hydraulic compositions.

22. A hydraulic composition comprising a hydraulic material and the dispersant of claim 20 or 21.

23. The hydraulic composition of claim 22, which is a cement composition or a gypsum composition.

24. A method for producing the composition according to any one of claims 13 to 19, and

comprising a step of reacting the lignin sulfonic acid compound with the aromatic water-soluble compound to obtain the lignin derivative.

25. A method of making a composition, the method of making having:

a step of preparing a liquid composition containing a lignin derivative as a reactant of a lignosulfonic acid-based compound and an aromatic water-soluble compound, and

drying the liquid composition to obtain a dried solid;

the dry solid satisfies the following conditions (A) and (B), and is a granular material:

condition (a): the average particle diameter is in the range of 30 to 250 μm,